THE PHOSPHONOUS ACIDS AND THEIR DERIVATIVES', ARLEN W . FRANK Research Center, Hooker Chemical Corporation, Niagara Falls, Neto York Received November 16, 1980 CONTENT8
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .............................................
390 390
.....................................
391
(c) With carbonyl compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .392 .
B. Reactions of phosphonous acids
,
. . , , . , . . 396
bons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...........................
.....................
401
.................... 6. From phonphonous diesters.
. . . . . . . . . . . . 404 3. Phosphorobenecne and related compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404 4. Reaction with pseudohalogen compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405 406 6. Addition of oxygen, sulfur, or selenium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405 6. Addition of halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7. Other addition reactions ................................ 8. Condcnsationa in which new carbon-phosphorus bond is formed . . . . . . . 406 (a) Phosphinous compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
* This review WBB prepared, in part, while the author was employed at the Carothers Research Laboratory, E. I. du Pont de Nemoum and Company, Wilmington, Delawftre. 389
ARLEN
W. FRANK
CONTENTS (Continued)
406 407 407 408 . . . . . .. . . 408 408 408 2. From trialkyl phosphites with Grignard reagenta . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . 408 3. From phosphonous dichlorides.. .......... ........................ 408 409 4. From other phosphonous diesters. . . . . . . . . . . . . . . . . 409 409 .................. 409 400 411 41 1 412 412 7.Related reactions, ......,........ 412 ............................ . . . . . . . . . . . . . . . . . ~412 412 B. Reactions.. . . . . . . . . . ... .. . 412 412 B. Reactions.. . . . . . . . . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413 VII. Phosphonous ester chlorides, amide chlorides, and ester amidcs . . . . . . . . . . . . , . . . . 413 A. Phosphonochloridous esters. . . , . . . , . . . . . . . . 413 414 414 414 415 A. Synthesis of phosphonous monoesters. . 415 415 2. From phosphonous dichlorides.. . : . . . 415 415 4. From phosphonous acids.. . . . . , . , . . . , 416 1. Addition of sulfur., , . . . , . . . , . , . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . 417 . . . . . . , . . . . . . . . . 417 2. Reaction with halogens.. . . . . . , . . .. 417 417 . . . . . . . . . . . . . . . . 418 418 418 418 418 418 ...................... . . . . . . . . . . 418 B. Reactions of DhosDhonous anhydrides., .. - XI. Eleferenccs. . , , , . . . , . . . . . . . . . , . . . . . . . . . ....................................... 419
. .
..
.
. ..
. .. . .
.
. . . . . ... . . . . . . .. . .
.. . . ... I
. . .
I
.
I
..... . . . . .. . . . . .. .. . . .. . . .. . . . . . . . . . .. . . . . . . . . . .
.. . .
I. INTRODUCTION A. ffENERAL
The phosphonous acids (RP02H2)are the organophosphorus members of the group of substances known as the lower acids of phosphorus. They contain one carbon-phosphorus bond and occupy a position intermediate between the phosphonic acids (RPOaHz), in which the phosphorus is fully oxidized, and the primary phosphines (RPH2),in which it is fully reduced. A characteristic feature of the lower acids of phosphorus is their tendency to assume whenever possible a form in which the phosphorus is tetravalent and to exhibit one less acidic function than might be expected. The phosphonous acids also show this behavior. Of the tautomeric structures that can be written, I1 re-
flects the monobasic character of the phosphonous acids and is a better representation of the free acids than I. R-P
/OH ‘OH I
0 7
R-F’4H
H ‘ I1
The derivatives of the phosphonous acids, however, may be subdivided into two broad classes: derivatives based on the trivalent structure (I) and derivatives based on the tetravalent structure (11). Derivatives in which both hydroxyl groups have been replaced contain trivalent phosphorus, whereas derivatives in which only one hydroxyl group has been replaced exhibit the behavior of compounds in which the phosphorus is
39 1
THE PHOSPHONOUS ACIDS AND THEIR DERIVATIVES
tetravalent. Their chemistry is quite different, as will be seen in this review. E. SCOPE AND LIMITATIONS OF PRESENT REVIEW
The literature on the phosphonous acids has not previously been explicitly reviewed. Surveys of work done prior to 1850 may be found in texts by Kosolapoff (175), Fox and Lockhart (81), Goddard (98), and Plets (272). Related topics appearing more recently in reviews are the phosphonic and secondary phosphinic acids by Kosolapoff (176), the phosphonic acids by Freedman and Doak (86), and the secondary and tertiary phosphine oxides by Berlin and Butler (36). The present review covers the synthesis and reactions of the phosphonous acids from their discovery through 1959,Following the section dealing with the phosphonous acids themselves are separate sections on their acid chlorides, esters, thio esters, amides, and anhydrides. Looked at in another way, the review covers all of the organophosphorus compounds that contain a single phosphorus-carbon bond with the exception of the primary phosphines (RPHJ, the phosphonic acids (RPOJI,), and the newly discovered primary phosphine oxides (RPOHZ). The basic plan of this review may be briefly outlined as follows: Synthetic methods used to prepare the phosphonous acids and their derivatives are described in detail. Syntheses in which a carbon-phosphorus bond is formed are described first, followed by syntheses from compounds which already contain a carbon-phosphorus bond, Syntheses in which a second carbon-phosphorus bond is ruptured are described last. All of the phosphorus compounds (of which the author is aware) known to have been synthesized by each method have been included in the text or listed separately in tables, depending on their number. Reactions of the phosphonous acids and their derivatives are described only in general terms, but an effort has been made to provide a complete list of references for each reaction. The order of presentation follows the same rule as given above for the syntheses, with the added proviso that reactions involving no valence change of phosphorus are described first. C. NOMENCLATURE
The nomenclature of the organophosphorus compounds described in this review follows in general the system adoptcd by the American Chemical Society’s Committee on the Nomenclature of Organic Phosphorus Compounds (7). Unfortunatcly, this report does not state whcther compounds containing the P-OII P(0)H system should be named as compounds of trivalent or of tetravalent phosphorus, i.e., whether thcy should be named as derivatives of phosphonous acid, (I-IO)J’II, or as derivatives of phosphinic acid, HOP(0)H~.The author has arbitrarily selected the
former because “phosphonous” unambiguously denotes a single class of aubstinces, whereas “phosphinic” is more often associated with secondary organophosphorus compounds than with primary compounds. However, the use of “primary phosphinic” is also considered correct. The use of the phosphonous nomenclature should not, of course, be construed as a plea for the adoption of the trivalent form for the phosphonous acids or their derivatives. It is used simply to avoid ambiguity.
11. PHOSPHONOUS ACIDS The phosphonous acids are monobasic acids of the formula RPH(0)OH. Most of the aromatic members are crystalline and are easily characterized by their melting points. The aliphatic members, however, are usually liquid, and since they easily undergo disproportionation on heating cannot be purified by distillation. Only one phosphonous acid, C,F,PH(O)OH, has a recorded boiling point (table 3). Many of the liquid phosphonous acids for which no data are given in the tables have been characterized instead by refractive index or density. A. SYNTHESIS O F PHOSPHONOUS ACIDS
1. From elemental phosphorus
(a) With acetone In 1864 it was reported that the distillation of acetone with iodine and elemental phosphorus gave an oily phosphonous acid believed to be 2-oxopropylphosphonous acid (263). The acid formed an amorphous barium salt, soluble in water and insoluble in ethanol. No work has been done since to verify this reaction.
(b) With olefins and oxygen Solutions of olefins and white phosphorus in benzene or petroleum ether rapidly absorb oxygen and deposit crystalline “phosphorates,” which cont,ain phosphorus and oxygen in a 2:4 ratio (258,289,333,350,351,352). These, on treatment with water, are hydrolyzed to 8hydroxyalkylphosphonous acids (258, 351, 352). The intermediate esters can be isolated by salting out with ammonium chloride (351). RCH=CHt
+ 3P4 + 20% -+
RCH-
CHa
I
0
0 1
\p/-P=o \I H
0
3 ’RCHCHzPOZH2 I
RCHOHCHlPOrHl -t Hap04
bP(O)(OH)%
Willstatter claimed that he had prepared an intermediate “phosphorite” having one less oxygen atom than the phosphorate, but later work has not substantiated t,his (333). However, olefins whose phos-
292
ARLEN W. FRANK
phorates are not insoluble absorb one more atom of oxygen, giving compounds of the formula RPzOs (333). Few phosphonous acids have actually been prepared and characterized by this method. The phosphorates have generally been characterized by oxidation with nitric acid to the phosphonic acids. The “phosphorates” and “phosphorites” described in this work are apparently identical to those prepared by the reaction of olefins with phosphorus trichloride and acetic anhydride (Section II,A,2), though the proposed structures are different. A new polymeric structure has recently been proposed (333). 2. From phosphorus trichloride, olefins, and acetic anhydride Olefins react with phosphorus trichloride and acetic anhydride giving crystalline “phosphorites,” which are converted to a,@-unsaturated phosphonous acids on hydrolysis (320, 321). Overall yields are in the order of 50-60 per cent. RCH4Hi
+ 2PCl1 + 3(CH&O)aO
--+
RCH-CHI I
b
I
0-P
‘PL’ 2Hr0
+ RCH=CHPOzHn
3. From hypophosphorous acid or its salts
(a) With olefins Sodium hypophosphite adds to olefins in the presence of free-radical initiators, giving sodium salts of phosphonous acids (316,325). Initiators that have been used are di-tert-butyl peroxide and 2,2-bis(tert-butylperoxy)butane (325).
+ HzP(0)ONa
+
(b) With secondary or tertiary alcohols Hypophosphorous acid reacts with certain secondary and tertiary alcohols to give phosphonous acids (78, 79, 111, 323). The mechanism of this reaction is not clear. The reaction may proceed through the isomeriaation of an initially formed hypophosphite ester, but the presence of triphenylmethyl chloride as a by-product in the reaction of hypophosphorous acid with triphenylcarbinol makes a carbonium-ion mechanism more likely (111). The overall reaction is written as follows: (CsHs)rCOH
RCHzCHzPH(0)ONa
Products of this type have been prepared from l-hexene, l-octene, l-tetradecene, diallyl sulfide, and divinyl sulfide (325). The yields from the first two were quantitative. Hydroxy-substituted olefins, such as 3-buten-1-01 or methallyl alcohol, yield phosphonous acids which can be
+ HzP(0)OH
+
(CeHs)rCPH(O)OH
+ HIO
Substantial amounts of the corresponding hydrocarbons may also be formed, depending on the reaction conditions (78, 79). The phosphonous acids that have been prepared by this method are (CaHs),CPOzHz,m.p. 245-248”C., from triphenylcarbinol (78, 111, 323), and [p-(CH,)nNCaHI]gCHPO2H,, m.p. 9O”C., from Michler’s hydro1 (78). A crystalline phosphonous acid was also prepared from 1,2,7,8-dibenzoxanthol and hypophosphorous acid (79).
+ HIP08
If oxygen or air is passed into the reaction mixture the phosphorite redissolves and is oxidized to a “phosphorate,” but the product of hydrolysis is the same phosphonous acid. In this case the by-product is phosphoric acid. Both intermediates react with alcohols, giving ester derivatives which still contain two phosphorus a t o m (320, 321). These “phosphorites” and “phosphorates” are apparently the same intermediates as those obtained in the reaction of elemental phosphorus with olefins (Section II,A,l), though the structures given are different. The corresponding a$-unsaturated phosphonous dichlorides (RCH=CHPC12) can be prepared by a different method (Section III,A,9).
RCH=CHi
dehydrated on heating to cyclic esters called phostones (316).
(c) With carbonyl compounds Crystalline hypophosphorous acid adds to aldehydes or ketones when the reactants are heated together on the water bath for prolonged periods of time, forming a-hydroxyalkylphosphonousacids : RR’CO
+ HnP(0)OH
+
RR‘C( OH)PH(O)OH
Since the products still contain a replaceable hydrogen attached to phosphorus, care must be taken to prevent further reaction with the aldehyde or ketone. This is done by keeping the hypophosphorous acid in excess (328). This precaution is not necessary with ketones higher than acetone, since they do not form disubstitution products (213, 214). A list of the compounds that have been prepared by this method is given in table 1. (d) With Schiff bases Hypophosphorous acid adds to the C=N bond in Schiff bases in a manner similar to the reaction with carbonyl compounds described above. In practice it is not necessary to prepare and isolate the Schiff base; a mixture of hypophosphorous acid, an amine, and a carbonyl compound (often used in excess as the solvent) is heated for a few hours on a water bath, and the product usually separates in crystalline form. Only primary amines undergo this reaction. CHI (CHs)zCO
+ H*P(O)OH + RNH,
+
NHR
C \’ C H I \pH(O)OH
393
T H E PHOSPHONOUS ACIDS AND T H E I R DERIVATIVES
TABLE 1 Phosphonms acida prepared from carbonyl compounds
I
Phoaphonoua Acid
Carbonyl Compound
I
Yield
1
~
'I
T:;2
Referenoes
oc. (HOCHtP0tH)tCa . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CHICHOHPOIHI. loo-CtHtCH0HPO:H ........................... ~-CIHIICHOHPOIHI
..
~>HOHPO,HN~,
Trioxymethylene Acetaldehyde Iaovaleraldehyde Enanthaldehyde
Cryatallhe*
. . . . . . . . . . . . . . . . . . . . . 1,2,6,6-Tetrahydrobenraldehyde
........
CiHnCHOHPOtHr ....... .., ,.., ~-~Eo-CIHK~H~CHOHPOIH~ 1,3-CaHt(CHOHPOtHNa)i. . . . . . . . . . . . . . . . . . . . . . 2-HOCnHtCHOHPOiHi. ........................ Camphor-3-CHOHPOtHNa ...............
...
Bensaldehyde Cumaldehyde Isophthalaldehyde Salicylaldehyde (Hydroxy methylene) camphor
55-57
(315) (212, a m ) (212, 328) (114, 329)
236 (d.)
(301)
108 106 Crystalline*
(114, 217,328,329,330) (329) (114) (329) (114)
Crystalline*
(CHI)ICOHPO:HI.. ................ C:HO(CHI)COHPOIHI. ................ (CIHI)&OHPOIHI.. CIH,(CHI)COIIPOIHI CtHdCHt)COHPOtHi . . . . . . . . . . . . . . (CtH,)rCOHPOiHr ............................. CnHiCOHPOtH: . . . . . . . . . . . . . . .
Acetone Ethyl methyl ketone Diethyl ketone 2-Butanone Acetophenone Bensophenone Deoxybenioin
sa
CnH&Ht COHICOHPO:HI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bensoin or bensil
160 (d.)
CiHiCHOH 4-BrCnHtCOHPOtH: . . . . . . . . . . . . . . . . . . . . . . . . . .
4,4'-Dibromobenril
195 (d.)
~-CHIOC~HICOHPOIHI. ......................
o-Anlaoin, o-antsil, or o-deoxysniaoin
180 fd.)
~-CHIOCOH~CH: 3-CHtOCsHtCOHPOrH:,
m- Anisil
..
(208, 209, 217) (213, 217) (215, 217) (214, 217) (216, 217) (214, 217) (274)
I
I
I
4-Br CnHtCHOH
I I
.......................
3-CHtOCnHtCHOH
* No melting point given. Reactions of this type are listed in table 2. The reactants are listed instead of the products because of the complexity of many of the amines employed. Those amines noted more for their physiological activity than for their chemical behavior have been given their trivial names.
4. From phosphonous dichlorides Phosphonous dichlorides are readily hydrolyzed to phosphonous acids. Uusually dropwise addition to water followed by refluxing for a few minutes is sufficient. RPCI,
+ 2HsO
4
RPH(0)OH
+ 2HCI
Concentrated hydrochloric acid has also been recommended (335). For compounds which suffer scission of the carbon-phosphorus bond in acid solution, such as triphenylmethylphosphonous dichloride (1 11) and pdimethylaminophenylphosphonous dichloride (33, 40, 290, 307), aqueous alkali may be used. Pcrfluorinated alkylphosphonous dichlorides suffer scission of the carbon-phosphorus bond in alkaline solution but can be hydrolyzed with water (35,73,74). While seemingly straightforward, the hydrolysis of phosphonous dichlorides with water does not proceed entirely in accordance with the equation above. The
phosphonous acids, themselves odorlesa, are contaminated by an intense phosphine-like odor, and the yields (none given for any of the compounds in table 3) are less than quantitative. Hydrolysis with ethanol and water, though mentioned in the early literature (169,251), has been little used until recently (71,180). The products obtained by this method are odorless and the yields are improved. The method is made possible by the ease of hydrolysis of the partial esters initially formed in the reaction.
+ 2CsHsOH RPH(0)OGHs + HIO RPC&
4
+ CsHsC1 + HCl RPH(0)OH + CsHsOH
RPH(0)OCsHg HCI
The phosphonous acids prepared from phosphonous dichlorides by hydrolysiR are given in table 3. 6. From phosphonous esters The first ester group in phosphonous diesters is cleaved by a trace of mineral acid, but the second ester group is much more resistant to hydrolysis (305). Phosphonous acids may be prepared from phosphonous diesters or phosphonous monoesters by hydrolysis with concentrated acid or base (193,305). For a rCsum6 of older work on the hydrolysis of phosphonous monoesters see Section VIII.
394
ARLEN W. FRANK
TABLE 2 Phwphonous acids prepnrcd from Schifl bcrsss ~~~
~
~
PhosDhonoils Aoid Pwnarnd from 8chiE Bane of
-
~
-
Mdtini I'rdnt.
- .--
Carbonyl Compound
Amine
____-
-
" c.
Aniline Aniline Bensylamine Aminoguanidine carbonate dNHrSOrCaHdCHrNH, 4,4'-Diaminodiphenyi sulfone
Paraldehyde hsaldehyde Salioylaldshyde Benssldehyde Baliaylddehyde Paraldehyde
100 (d.) 160 226
Propylamine Isohexylamine Cyclohexylamine Stearylamine Aniline Bensylamine N,N-Diethyl-pphaoylanediamlns N,N-Diethyl-pphenylenediamine N,N-Diet hyl-ppheaylenediamine N-Ethyl-N-~2-hydroryethyl)-pphsnylenylenedi~mine pphenetidine pPhenetidine pDiethylamino-o-phenetidine pAminopheno1 pAminoaoetanilide pAminoacetanilide 4-Amin~2-chloroscetanilide pAminopheny1-1-pyrroli~ne Aminoguanidine carbonate Phenylhydrarlne Aminoantipyrine pAminobenrenesulfonamide ~-NH~SOIC~H~CHINHI 4,4'-Diaminodtphenyl sulfone ~,~'-CHICONHCIH~O;C~H~", Sulfapyridine Suifathiasole
Acetone Acetone Amtone Aoatone Acetone Acetone Acetone Ethyl methyl ketone Diaoetone aloohol Acetone Aoetone Acetophenone Aoetone Acetone Acetone Ethyl methyl ketone Acetone Aoetone Acetone Acetone
327 (d.)
Acetone
+
HIPO~ RPH( 0)OH
air 71
ea
e4 Good
An attempted carbylamine reaction with phenylphosphine, chloroform, and alcoholic potassium hydroxide gave instead phenylphosphonous acid (242). An alternative route to the direct oxidation of primary phosphines is halogenation to the phosphonous dihalide, followed by hydrolysis (Section 1111A,8). A list of the phosphonous acids prepared by the oxi-
206 210 (d.) 14.8 (d.) 200 (d.) 198
me
Good
185 (d.) 200 (d.) 232 (d.) 204 (d.) 101 (d.) 180 (d.) 184 (d.)
87 Good 85
+ RP( O)(OH)r
217 (d.) 208 214 (d.) 220 (d.) 218 208 210 210 180 (d.) 167 (d.)
Good
Acetone
Phosphonous acids may be prepared from primary organophosphines by carefully controlled oxidation. More vigorous oxidants, such aa nitric acid, yield only phosphonic acids (104, 119). In most cases air, oxygen, or hydrogen peroxide is suEcient. Phosphonous acids prepared from alkylphosphines are partially oxidized to the phosphonic acids during the oxidation, more so with nitrogen dioxide than with oxygen or 30 per cent hydrogen peroxide (44). Hydrogen peroxide at 8& 100°C. does not readily effect the oxidation. The use of acetic acid as a solvent and molybdenum oxide as a promoter is beneficial (44). The oxidation of alkylphosphines with air or oxygen yields phosphoric acid, the phosphonous mid, and the phosphonic acid in 3: 6: 1 ratio regardless of the temperature or the concentration of oxygen (44).
2
100 (d.)
ea
6. From primary phosphines
RPHI
isa
Acetone Aoekne Acetone Acetone Aoetone
Referenom
-- - __ -
ies
dation of phosphines is given in table 4.
7 . From higher organophosphorus compounds Reactions of this type are known only in the trifluoromethyl mries, and are due to the ease with which compounds containing the CFa-P system liberate fluoroform on aqueous or alkaline hydrolysis. Trifluoromethylphosphonous acid is obtained by the following reactions (35, 73) :
+ NaOH + HtO (CF:bP(O)H + HsO + (CF:):P
+
CFaPH(0)ONa
CFSH(0)OH
+ PCHF:
+ CHF:
B. REACTIONB OF PHOBPHONOUB ACIDS
The reactions of phosphonous acids which yield derivatives described in detail in other sections of this review are not considered here. These include the reaction with phosphorus trichloride to form phosphonous dichlorides (Section 111,A15)and the reaction with alcohols or with phosphonous diesters to form phosphonous monoesters (Section VIII,A,4). 1 . Disproportionation
The phosphonous acids, in common with other lower acids of phosphorus containing the tautomeric P-OH e P(0)H system, undergo a characteristic disproportionation reaction when heated by themselves to
-
THE PHOSPHONOUS ACIDS AND THEIR DERIVATIVES
395
TABLE 3 Plio~phonmiracih prepared from phosphonmcn dichlorida ~
Pbwphonous Dichloride
Phosphonoua Acid
.
. . . . ... . . . . . . . .. , , . . . . . .. . . . .. . , . . . . . . . . . ...., . . . . . . . . . . . . .
ino-CtII~P0:Hz. . . . . ho-Cdb~POrHr.. . ,
,
,
,
,
,
,
, ,
.
,
..
. . . . . . .. . . ...
4-ClCsHtPOrHr. . . . . .................... 4-BrCtHt POaHr . . . . . .................... ~ - C H I C O H ~ P O.~, H . ~. . . . . , . . . . , . . I . . . . . . . . . . 3-CH1CsHtPOtHr. . . , .......... 4-CH1CtHtP0r1Ir. . . . . . .... . , . . . . . . ,... . . ~-CI-~-CHIC~H~PO~H~. 4-CrH1CsHtP0rHr ..................................... 2,3-(CHa)rCsHiPOiHr.. . . . . . . . ,,, . .. , , . . . 2,4-(CH1)zCtHaP0rHr.. . . . 2,6-(CIIr)aCtHIPOrHa.. . ~-(~sc-CIHI)C~H~PO~H~. 2,4,5-(CH1)tCsHsPOrHt.
..
.
........
.
71
71/0.7 mm. (b.p.1
Cmklline* 84 166-167 126 -126
~ - C ~ H I C H ~ C H ~ C ~ H ~. P O : H ~ . ~-CIOHIPOSH~. . ...
OC.
128 147
2,4,8-(CIIi)1CsHrP0aHa.. ... . ... . . . . . . .. . .. . . . . . .. .... .
. ..............
per ccn,
Referenow
104-1 Ob 70 e344 43 100 CryBtsllinr+
. ... ... .
t,S(or 6,2)-C€11(iso-C:H~~CtRtPO~Hr. ... . 4-CdTsCsH4POrHr.. . . . , . . .. . . . .
Point
131 143
. .. . .. . . .. . . .
. ... . .
Yield
246-248 74-76 70, 86
.................................. ...................
CsHiCH=CHPOrHa CtHrPOrHr..
Melttng
..
I38 114-114.6 116 I26 70
~-(CHI)YNC~HIPO~H~. , . , . .. . ,, . . , , . . . , , . , . I-(CmHa)rNCaH~POaHt. 4-CsIW C H I ) N C ~ H ~ P O ~ R. .~ .. . . . . , . . . . . . . . . . , , . ~-C~R~CH~(CHI)NC~H~PO~H~. ~ - C H I - ~ - ( C H I ) ~ N C ~ H I P O. .~.H.~. ., , , . . . . . . . . . . . . .
162
.... . . . . .. . . . . . . . .. . .. . ~ - C H ~ ~ - ( C ~ H I ) ~ N C ~. R , .~. . P. O . ~ H ~. .. . . . . . . , . . . . . I
I
I
160.6 98
No melting point given.
about 150°C. (35, 73, 104, 169, 188, 189, 202, 228, 230, 234,235,236,238,240, 251,305). One mole of a primary phosphine is produced for every two moles of phosphonic acid:
5
BRPH(0)OH
RPHI
+ 2RP(O)(OH),
Until recently it W M believed that aliphatic phoephonous acids began to undergo disproportionation at a lower temperature than aromatic phosphonous acide, possibly as low as 60°C.(104), but this is not the case (305).
TABLE 4 Phosphonous acids prepared from primary phosphines
I
Phosphonous Acid
Primary Phosphine
Referem
-I
per cent
.
.
n-C~HlrPOrIIr. . . . . . . , . . . . . . n-C.HlrPOl€I: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C ~ H I C I I ~ P O.I.H. .~. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CSII~P01I1,. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-C H I C ~ H ~ P O I H ~. . , . . . . . . . . . , . . . . , , . . . . . . . . . . . . . . . ~ , ~ , ~ - ( C H I ) I C ~ H I P.O. Z. H . .~. .. , . , . . , . . . . . . . . . . . , . . . . . . . . . . ~ , ~ , ~ - ( c ~ ~ ~ ) ~ c ~ R ~ P o ~ B. ~. . ..... 2-CICsIItOCII~POrHa. ........,......... ..,.. ~-CICJI~OCH~PO~II~. ........................ 2,4-CIrCsIr,OCM~PO,Ht , . . . . , . . . . , , . . . . . . . . . . . . . . . . . . . , , . . . 2,4,6-C11CsHtOCHaP0~ ........................
. . .. . .
.
.
.
. .
. . . . .
.
.
. ..
I . , . . . . . . . . . . . .
. . I
..
122-124 100-101 129-130
396
ARLEN W. FRANK
When used for the synthesis of an organophosphine, the phosphonous acid is usually heated rapidly to 250°C., at which temperature the organophosphine distils. The phosphonous acid may be generated in situ by treatment of a phosphonous dihalide with ethanol, and converted directly to the phosphine by distilling to dryness (169, 188, 202, 228, 230, 246, 251). It is,advantageous to add sodium carbonate to trap the phosphonic acid, which might otherwise break down to metaphosphoric acid and the hydrocarbon (202). Kosolapoff and Powell (180) suggested, on the basis of molecular-weight determinations on phosphonous acids which showed that they were in a state of trimeric aggregation, that disproportionation may be the result of a rearrangement of the protons and oxygen atoms within the cyclic trimer in such a way as to produce the maximum concentration of oxygen a t two of the three phosphorus atoms. The only known exceptions to this disproportionation are acids which break down in other ways at temperatures below the disproportionation temperature, such as the p-dialkylaminophenylphosphonous acids (307) or the a-hydroxyalkylphosphonous acids (209, 328), which suffer scission of the carbon-phosphorus bond. 2. Scission of the carbonphosphorus bond
Some phosphonous acids undergo scission of the carbon-phosphorus bond a t temperatures below the disproportionation temperature. p-Dialkylaminophenylphosphonous acids, alone among the aromatic members, break down when heated in neutral or acid solution as follows (207, 307) : p-(CH&NC6HcPOsH,
+ &O 2
+
(CHI),NGH~ Hap01
The acids, however, are stable to alkaline or alcoholic solution (307). When heated by itself p-dimethylaminophenylphosphonous acid yields a variety of decomposition products including dimethylaniline, metaphosphoric acid, phosphine, and elemental phosphorus (307). The a-hydroxyalkylphosphonousacids as a class undergo scission of the carbon-phosphorus bond under relatively mild conditions (209, 328). On stronger heating, phosphine is evolved and metaphosphoric acid is left (328). Triphenylmethylphosphonous acid suffers scission of the carbon-phosphorus bond in acid solution giving triphcnylcarbinol, and in alcoholic sodium ethoxide giving triphcnylmethane (111). The acid is stable, however, to aqueous alkali. Phosphonous acids containing fluoroalkyl substituents are unstable to hot water or aqueous alkali (34, 35, 73, 74, 195). 3. Oxidation
The reducing power of phosphonous acids is characteristic of compounds Containing the P-H group. Phosphonous acids reduce ammoniacal silver nitrate to metallic silver (209, 230,240, 328), cupric salts to metal-
lic copper (209), ferric salts to ferrous (209), mercuric chloride to calomel (73, 74, 209, ,210, 230, 240, 251, 252, 307, 328), and sulfur dioxide to elemental sulfur (230, 240); they react with metallic zinc and iron, evolving hydrogen (230, 240, 328). The phosphonous acids are oxidized in the process to phosphonic acids. Oxidant systems which have been found useful in preparative work are iodine/acetic acid (1 1 1), iodine/ sodium bicarbonate (74), mercuric chloride (210, 213, 214,215,217), alkaline permanganate ( l l l ) ,50 per cent hydrogen peroxide (74), bromine water (211, 212, 213, 214, 215, 217), and nitric acid. The use of more dilute hydrogen peroxide for the synthesis of phosphonous acids from organophosphines was noted in Section II,A,6. Nitric acid has been found useful with aliphatic phosphonous acids because of the high stability of the products toward oxidation (44, 104, 233), but aromatic phosphonous acids may suffer nitration of the ring in the process (28, 251). Electrolytic oxidation has been attempted unsuccessfully (210).
4. Reduction Phosphonous acids are not readily reduced to the primary phosphines. The classical reducing agents, such as sodium/alcohol, zinc dust/alkali, amalgamated zinc/hydrochloric acid, red phosphorus/iodine, etc., are ineffective (84). The reduction has, however, recently been accomplished with lithium aluminum hydride, phenylphosphine being obtained from phenylphosphonous acid in 13 per cent yield (341). 6. Reaction with halogens
Phosphonous acids do not react with chlorine in the cold, but on warming a violent reaction takes place with evolution of clouds of hydrogen chloride and bursts of flame (230, 240, 251). The residue is a mixture of charcoal and phosphonic anhydride. These phenomena are probably the result of reaction of the chlorine with primary organophosphinesproduced from the phosphonous acids by disproportionation (230, 240). The use of bromine water for the oxidation of a phosphonous acid has already been described (Section II1B,3). 6. Condensation reactions
The phosphonous acids contain a reactive hydrogen attached to phosphorus which can be replaced by alkyl groups in reactions similar to those used to prepare the acids themselves. One such reaction is the free-radicalinitiated reaction of sodium n-hexylphosphonite with 1hexene (325) :
+
CsHlaPH(0)ON~ C4H,CH=CH2
(CsHId2P(O)ONs
Secondary phosphinic acids are also formed in the reaction of a-hydroxyalkylphosphonous acids with aldehydes or acetone (209, 216), but not with ketones
THE PHOSPHONOUS ACIDS AND THEIR DERIVATIVES
higher than acetone (213, 214, 216) : (CHJzCOH (CHs)sC(OH)PH(O)OH
+ CsHsCHO
=p,,o€l CsHbCOH
7. Reactions not involving the phosphorus a l m Few reactions of phosphonous acids are known which do not involve the phosphorus atom. pBromophenylphosphonous acid when heated with ammonium hydroxide and cuprous oxide in a sealed tube a t 150OC. gives paminophenylphosphonous acid, m.p. 169OC., in 54 per cent yield (163, 164). The yield drops to 40 per cent if pchlorophenylphosphonous acid is used (164). The hydroxyl groups in a-hydroxyalkylphosphonous acids (328) or 8-hydroxyalkylphosphonous acids (258) can be acetylated without affecting the acid groups.
111. PHOSPHONOUS DIHALIDES The lower alkyl phosphonous dihalides are waterwhite liquids with obnoxious odors; they rapidly deposit amorphous yellow solids on exposure to air (80, 158), but can be stored indefinitely in an inert atmosphere (80). The tendency to form a yellow solid decreases with increasing chain length. Phosphonous dibromides are unstable to sunlight (246). A. SYNTHESIS O F PHOSPHONOUS DIHALIDES
1. From aromatic hydrocarbons (a) With Friedel-Crafts catalysts The Friedel-Crafts reaction has been used extensively for the synthesis of organophosphorus compounds for over eighty years and is still one of the best methods for preparing the aromatic compounds. The catalyst usually employed is anhydrous aluminum chloride, though ferric chloride has been found to be effective with phenolic ethers (330, 331). RH
+ PCls
AlCla -----f
RPCI?
+ HCI
For best results the aluminum chloride should be present in slight molar excess over the aromatic hydrocarbon (45). The yield falls sharply if the amount of aluminum chloride present is less than one-third of the molar amount of the aromatic hydrocarbon (175, p. 44). This, together with the stability of the complex formed between the aluminum chloride and the product, made the reaction a very inefficient one until recently; yields reported in all of the earlier work are low because most of the product was tied up as the complex. This problem has been solved by the addition of phosphorus oxychloride to the reaction mixture at the end of the reaction (45, 71, 72). The phosphorus oxychloride forms a granular complex, AICla* POCla, with
397
the catalyst which can easily be removed by filtration. With this technique 64-78 per cent yields of phosphonous dihalides are common (45, 46). The only known failure has been with naphthalene, which forms too stable a complex. The complexes may also be decomposed with water (in sufficient amount to break the complex but not to hydrolyze the phosphonous dihalide) (71, 72) or with pyridine (71, 91, 92). If the phosphonous dihalide is to be used for the synthesis of phosphonous or phosphonic esters, the complex may be decomposed with an alcohol or phenol (353) or with chlorine followed by an alcohol or phenol (178, 179). If the reaction is carried out in the presence of an aliphatic hydrocarbon containing a tertiary carbon atom, such as methylcyclohexane or isopentane, the phosphonous dihalide is found to be reduced to the primary phosphine (308). The reaction of benzene with phosphorus trichloride and aluminum chloride, for example, yields phenylphosphine when the reaction is carried out in the presence of methylcyclohexane. The use of prolonged refluxing periods as described in the early literature is not necessary except in the case of sluggishly reacting compounds, such as the halogenated aromatic hydrocarbons, and may lead to the production of substantial amounts of phosphinous halides as byproducts. With aromatic hydrocarbons containing several alkyl substituents the diary1 compounds constitute the major (235, 236) or only (82) reaction products, In one case a triarylphosphine was found (252). A serious disadvantage of the Friedel-Crafts method is that mixtures of isomers are often obtained. For example, in toluene the o :m :p orientation of substitution was found to be 10:27:63 (177). Another disadvantage is the well-known tendency of aluminum chloride to isomerize aromatic hydrocarbons. The reaction of n-amylbenzene with phosphorus trichloride and aluminum chloride gave 5 per cent of tert-butylphenylphosphonous dichloride in addition to the normal product (45). In other reactions the alkyl substituent has been split off (45). Other variations of the Friedel-Crafts reaction involve the use of aliphatic hydrocarbons containing six carbon atoms or more (353) (those with less than six carbon atoms tend to deposit large amounts of free phosphorus) and the use of phosphorus tribromide instead of phosphorus trichloride (190, 191)., Phenolic ethers such as anisole or phenetole are cleaved by strictly anhydrous aluminum chloride, but not by ordinary anhydrous aluminum chloride (184). The cleavage products are arylphosphorodichloridites, ArOPC12. Failure to take part in the Friedel-Crafts reaction has been reported with stilbene (238), anthracene (257), ethyl a-naphthyl et8her (184), acetophenone (234), benzophenone (234), ethyl benzoate (234), dibenzylaniline (330), phthalanil (330), benzonitrile (234),
398
ARLEN W. FRANK
iodobcnxene (234), and trichlorobenzene (179). A list of the successful reactions is given in table 5.
(b) With no catalysts Certain aromatic hydrocarbons can be made to react with phosphorus trichloride in the absence of a catalyst. Dimethylaniline, for example, is sufficiently reactive to condense with phosphorus trichloride at the reflux temperature (33,40,290,330), giving pdimethylaminophenylphosphonous dichloride in 60-65 per cent yield. The dimethylaniline is used in sufficient excess to trap the hydrogen chloride produced. 2(CH,)rNCsHs
+ PCl,
+
p-(CH,)sNCaH,PCh
+ (C H ~ ) ~ N C *HCl ~HII
Other dialkylanilines have been used, including two N-alkylcarbazoles (33, 50). Benzene reacts with phosphdrus trichloride when a mixture of the two substances is passed through a hot tube at 600OC. (226, 230). The mixture is recycled for several hours and the heavier phenylphosphonous dichloride is drawn off from time to time. Small amounts of phosphorus and biphenyl are obtained as by-products (166). Numerous improvements on the original procedure of Michaelis have been described (8,41, 71, 188, 192,224,274), dealing principally with the design of the apparatus. Yields are of the order of 50 per cent (230). Other than benzene, the only aromatic hydrocarbon
TABLE 6 Phosphonm dihalides prepared from aromatic hydrocarbons with Friedel-Crafts catalysts Preparation from Phoaphonous Dihdide
Aromatic hydrocarbon
-
Yield
PXl
Melting Point
Boiling Point
-00.
Ben Iene
PCll
80
OC. 8&82/10 mm.
.. , . , . . , . , . . . . . .
Chlorobenzene
PCll
72
253-255
. . . . . . .. . ... ... . . . .. . . . Z-CHICIH~PCIS.. . . . . . . . . . . . . . . . . . . . . ~ - C H I C ~ H ~ P C. I. S . .. . . . . . . . . . . . . . . . . . . . . ~ - C H I C ~ H I P .C .~. ~. . . . . . . . . . . . . . . . . . .
Bromobensene
PCIl
26
271-272
Toluene Toluene Toluene
PCII PClI PClI
20
244 235 246
psr cen
CiHrPCla ..............................
4-CICsHtPCla. . . ,
...
,
, ,
~ - B C I H I P C ~ :. . ,
, ,
,
,
................. Toluene . . . . . . . . . . . . . . . o-Chlorotoluene Ethylbenzene
PBri PClI PCl:
. . .. . . . . . . . . . 2,5-(CIIt~lCn€IIPCl1.. . . . . . . . . . . . . . . . . . . . 3,5-(CHi)tCsHiPCla. . . . . . . . . . . . . . . . . . . . ~ - C I H I C ~ H ~ P C.I I.. . . . . . . . . . . . .
o-Xylene m-Xylene pXylene m-Xylene n-Propylhenzene Cumene
PClI PClI PClI PClI PClI PClI
Z,~,~-(CHI)ICOHIPCI~ 2,4,6-(C1It)1CsII>PCli 4-CtHpCsH4PCh. , . . . . . . , . , . . . . , . , . . . , C(aec-CtHo)CsIItPCla. . . . , . , , . . . . . . . . . . ~ - C H I - ~ - ( ~ ~ O - C I H I ) C ~ N, I.P. C . , I.Z. . . . . . . 4-CsHiiCsH4PClr ................ ( C ~ H I I ) I C ~ I ~ P C. ~. . ~. ,. . . . . . . . . . . . . . I-(n-CsHir)Cs€ItPCls. . , . . . . . , . . . . . . . . . , 2-CloHIPClr. , . . , . , . . , , . . . . . , . . . . , . ........................ ................. ..... ~ - C ~ H & H Y C ~ H I P. .C. ~. .Z . . . . . . . . . . . . . , ~ - C ~ H ~ C H ~ C H ~ C O. ,H. ,I.P, .C. ~.~. . . . , , ~-CHIOCEHIPCI:. . . . . . . . . . . . . . . . . , . . ,
Pseudocumene Mesitylene n-Butylhenaene see-Butylbensene pCymene n-Amylbeneene rec-Amylbenzene Diarnylbenzene n-Hexylbenzene Naphthalene Naphthalene Biphenyl Diphenylrnethane Bibenryl Anisole
PClI PClI PClr PClI PClI PClI PClI PClI PClI PClt PBri PClI PCll PClI PClI
4-CtHs0CsH1PClr . . . . . . . . . . . . . . . . . . . . . . . Z.~-(CHIO)IC~HIPCII. , .. .. , . , ,,......,.. 4-CsI€sOCaHtPClz. , . . . . , . . , , , , . , , . , , , Dihenrofurand-PCII . , , , , , , , . . . , . . . . . , 4-(CHi)rNCsH4PCIa, . , . , . , . . . . , . . . . . . 4-(CaH1)zNCoIlrPCla. . . . . . . . . , . . . . . . . . . . 4-CsHr(CH1)NCaHtPClr.. . , . . . . , . , . , . , . , ~ - C ~ H ~ C H ~ ( C H I ) N C ~ .H. .I .P C ~ ~ . 4-CsHiCHa(C:Ha)NCsHiPCla. . . . , , . . . . , . Thiophen-2-PClt . . , . . . . . . . . . . . . . . . , . ,
Phenetole 1,3-Dimethoxybenzone Phenyl ether Diphcnylene oxide Dimethylaniline Diethylaniline N-Methyldiphenylamine N-Benzyl-N-methylaniline N-Benzyl-N-ethylsniline Thiophene
PCll PClI PClI PClI PClI PCII PC11 PClI PCll PCll
4-cH1CaHaF'Brr.. 3-CI-4-CHrCaHiP
...,...........
4-CaHrCsHtPClr .
2,3-(CH1)aCsHrPCls. . . . . . .
,
.
~ - ( ~ ~ O - C I H ~ ) C ~ I. I. I. P. .C, .I ,~... . . . . .
. .
. ..
.
...
..
.. .. . .
.
.
.
References
-
66
25
160-161 265-266
15 70 30 30
250-262
-30
47 64
127-131/5 mm. 268-270
30 8
35-37
39 33 7 22
50 15
6 15 20
278 257 253-254
58-59 65-68 5 2
35
279-280 273-275 116-119/1.0 mm. 116-120/1.5 mm. 275-278 130-210/20 mm. 118-121/1.0 mm. 160-250/20 mm. 146-149/1.5 mm. 180/10 mm. 200-220
221/20 mm. 250/60 mm. 140-140.5/11 mm. 266 (d.)
27 14 7 25 32
Low -
147
175-180/12-15 mm,
ZOO/lZ mm. 66
245-250/25 mm. 158-100/0.6 mm.
(45, 46, 71, 71, 81, 103, 134, 141, 174,178,201,232, 234,330, aaa, aea) (28, 30, 173, 178, 234, 236,265) (63, 134, 234, 136, 330) (177, 234) (177, 234) (45, 48, 103, 134, 161, 177, 179, 190, 201, 204, 232, 234, 247, 250,261,287,337) (190) (225) (45, 46, 128, 134, 235, 348) (236, 343) (234, 250, 343) (130, 134, 234, 344) (343, 344) (45) (45, 46. 134, 175, 234, 236) (234, 236) (60,234, 236) (45) (45) (234, 236, 251) (133) (45) (133) (45) (191, 342) (191) (192, 238) (234, 238) (234, 238) (63, 128, 134, 142, 184, 234, 330) (234) (331) (64, 134) (66) (57, 101, 252. 307) (252) (252) (252) (2521 (304)
399
T H E PHOSPHONOUS ACID8 AND THEIR DERIVATIVES
to which this procedure has been successfully applied is thiophene (304). 2-Thienylphosphonous dichloride, b.p. 218OC., was obtained in 6 per cent yield. Toluene gave, in addition to much bibenzyl, stilbene, and phosphorus, a trace of a tolylphosphonous dichloride believed to be the meta isomer (235, 247).
2. From organometallic reagents Grignard reagents and organolithium compounds react with phosphorus trichloride, giving exclusively tertiary phosphines (80, 340). Even under the most favorable conditions it has not been found possible to prepare phosphonous dichlorides by this method. One must therefore have recourse to milder organometallic reagents. In recent patents, however, the use of a complex of the Grignard reagent with an oxygen or nitrogen heterocycle was said to give a phosphonous dichloride with phosphorus trichloride (288). The syntheses of C8H~,PClz and pClgHa~CeHdPCl2were cited as examples. Historically, the oldest and most important of these are the organomercury compounds. Michaelis used this method to synthesize aromatic phosphonous dichlorides of unambiguous structure for comparison with the products obtained from the Friedel-Crafts reaction. It was also until recently the only method available for the synthesis of aliphatic phosphonous dihalides. The reaction is usually carried out in sealed tubes at high temperatures (230-250OC.) to destroy the unreactive RHgCl by-product which might otherwise contaminate the product (104, 233). &Hg + PCla -+ RPCli + RHgCl In a few cases the mercury in the organomercury compound was entirely converted to mercuric chloride (234, 251). The method does not work well with phosphorus tribromide because of the difficulties of purifying the phosphonous dibromide (104). Grignard reagents may be used if they are first converted to organocadmium compounds (RZCd) or to organozinc compounds (RZnBr) by reaction with cadmium chloride or zinc chloride. Fox (80) prepared a series of n-alkylphosphonous dichlorides in 2 6 4 7 per cent yields by the reaction of phosphorus trichloride with dialkylcadmium compounds a t -2OOC. RzCd
+ 2PC&
-+
2RPCli
+ CdCll
This reaction, however, gives satisfactory yields only with aliphatic compounds (340). The organozinc bromides, on the other hand, are useful for the synthesis of both aliphatic and aromatic phosphonous dichlorides (340). RZnBr
+ PCla
-+
RPClz
+ ZnBrCl
The organozinc compound is added in the form of a slurry to the phosphorus trichloride in boiling ether. The compound is used in the form of RZnBr rather than
RzZn, because the latter compounds are much more reactive and give exclusively tertiary phosphines (233, 340). A parallel can be drawn with the organomercury compounds, which are reactive in the form RzHg and unreactive in the form RHgCl. A newer method which gives excellent yields (7385 per cent) of aromatic phosphonous dichlorides is the reaction of an aryltrichlorosilane (or diaryldichlorosilane) with aluminum chloride a t room temperature, followed by reaction of the arylaluminum halide with phosphorus trichloride (360, 361, 362).
+ AICI, RAlCla + PCla RSiCla
-+
+
+ SiCl, RPClt + MCl, RAlClg
The aluminum chloride is separated from the product in the usual manner by complexing with phosphorus oxychloride, as done in the Friedel-Crafts reaction (Section III,A,l,(a)). Another method involving organoaluminum compounds is the reaction of an aluminum trialkyl with phosphorus trichloride (267, 363, 364). The yield is much improved if the aluminum trialkyl is first complexed with ether or pyridine (267). RaAl
+ 3PCla
-+
3RPCIz
+ AlCla
The alkyl radical is not isomerized in the reaction. The method failed with the lowest alkyl member, aluminum trimethyl, as the methylphosphonous dichloride could not be separated from the reaction products (267). Ethylphosphonous dichloride may be conveniently prepared by the reaction of an organolead compound, tetraethyllead, with phosphorus trichloride (158, 159, 160). The reagents are heated under reflux for 30 hr., and the yields are quantitative. (CZH6)dPb
+ 3PCh
--*
3CzH5PC1,
+ PhC1z + CzHC1
No reaction occurs with tetraphenyllead (51). Syntheses of a few phosphonous dibromides have been reported in which phosphorus tribromide was substituted €or the trichloride in reactions with organomercury compounds (104, 246) or organolead compounds (302). Furthermore, a reaction of phosphorus tribromide with an organotin compound was reported (302) which failed to take place when phosphorus trichloride was used. ( CzH&Sn
+ PBra
-+
CZHsPBrZ
+ ( CZH5)2SnBr
In addition to the reactions described, displacement reactions with phosphorus trihalides also occur with the more metallic elements of the phosphorus subgroup. Phosphorus trichloride will abstract a phenyl group from triphenylbismuthine and from triphenylstibine, but not from triphenylarsine (51, 52). The phosphonous dihalides prepared by the reaction of phosphorus trihalides with organometallic reagents are listed in table 6.
400
ARLEN W. FRANK
Preparation from Phosphonoua Dihalide
Melting Point
Organometallia reagent
Boiling Point
Refermaw
Organomemury method par ccnf
.. ..
.
. . . . . ... .. . . .. . . . CtHaPCh. . . . . . . . . . . . . . . . . . . . . CrHaPCIr. . . . . . . . . . CHFCHPCI~. . . . . , . . CaHiPClr. , . . . . , . . ,
PCII PClI Pclt PClI PclI PCla
OC.
114-117 l04/760 mm. 140-143 13S-138 157-150/7S0 mm. 15bl57 180-183 llb111/12 mm. 220 255-257 101-103/S mm. 244 236 246 258-258 280 250 180/10 mm.
so 81
PCI~ PCll PCla PBra Pcla PCll PCla PCll PClI PCll Pcll PCll Pal PClI PClI PCla
. . . . .. . . . .. .. . . . . . .. . . . . . .. . . . . . . . . . . . .. . . . .. . . . 4-(CHa)iNCtHtPClr. . . . . . . . . . . , ~ - C ~ H I ( C H I ) N C ~ H I P.C . .I.~. .. . . CaHgPBrr , . . . . . .. . .., 3-clCtH1PClr. . . , . . . . . . . Z-CHICtHtPClr 3-CHCtHtPCla. . . . . . . . . . . ~ - C H O C I H I P C ~ ~. ... . . . . 2,4-(CHdrCt€laPclr. ... 2,4,5-(CHa)aCtHrPClr. ... 1-CioHIPClr. . . . . . . . . . . . . . . Z-CioHiPCli, , . , . . . . . ,, 4-CHaOCaHtPClr. . . . . . . . . .
31 16 Low 78 86
so
250/12S mm.
(104, 233) (31, 140) (104) (104, 233) (70) (104) (161) (132) (230, 245) (248) (355) (235. 261) (235) (234, 251) (56, 343) (236) (152) (191) (234) (234) (252, 307) (234)
Organoasdmlum method
. . .... . . . . . . . . . . . . . .. . . . . . . . . . . . ... . . . . .. . . . . . . . . . . . . ........ .... . .. . . . . . . . . . . . ... .. . . . .. . . .. . .. . . . . . . . . . . ... .
CIHIPCIS, , .. CaH~Pcli.: . . . . ... Iao-CaHYPCl,. . . . ... . . . . CcHvPClr . .. .... . iaoGtHtPClr. . .. . CgHiiPCIi.. . . . . . . . n-CaHiiPclr. . . . . .... . . . n-C~HrlPClr.. . . . , . . . . . . , . , . n-CaHirPClr, . . .. . . .. 1-CioHiPCIr.. . . . . . . .. .
PClr
112 134.8 41-42/17 mm. 58-60/22 mm. 48.5-49/12 mm. 184
PCla PCla PClI
228.6 247 118-120/0.5 mm.
I
208
I
Orgsnoaina method
. . .......... .. .. .. . .. . . . . . .. . . ... . . . . . . .
CtHaPcla , , . . CvHiiPClr . . ..... , .. .. CaHtCHrPClr. . . . . . . . . . . . . . . C,H&PClr. . . . ... .... . CBrCsHtPClr . . .... . . ~-CH~C~B~PC , .I.I... . . . , . . , . . . 4-CHgCtHtPClr. . , . , , , , , . , . . . . ~-CIHICIHIPCI:. .. . , . . , . . . I-CioHiPCIr. , . . . .. ... 2-(3raHrPCl*. . . . . . . . . . I
I
. . . .. . . . .. . . . .. . . ... . ... . .. . . . ... ... I
CdHeZnBr CaHirZnBr CoHrCHtZnBr CtH6ZnBr 4-BrCaH12nBr 2-CHrCsHtZnBr 4-CHCtHtZnBr 4-CrHd3H1ZnBr 1-CioHIZnBr Z-CIoHvZnBr
PCll PCla PCh PCla Pcll PCla PCll PCla PCll PCIa
44 34 42 32 8
38 23 17 17 9
65-60
24 65
4141 -
74/33 mm. 93-94.6/12 mm. 118-119/12 mm. 99-lOl/ll mm. 65/0.8 mm. 127-129/12 mm. 116.5/11 mm. 85/0.4 mm. 136-137/0.S mm. llO/O.2 mm.
Organmilieon method ~~~~~
~~~~
~~~
CaHgPCll ...................... CtHiPClr ...................... 4-ClCtHtPClr... . . . . . . . . . . . . . . . 4-BrCaHtPClr.. . . . . . . . . . . . . . . . . CCHaCaRtPCIr ...........
CtHlSiClr (C6Ht)rSiclr 4-CICtHtSiCla 4-BrCtH1BiCla I-CHICIH~SICII
CrHgPclr ...................... C ~ H I P C...................... I~ Iso-CaHvPCIr . . . . . . . . . . . . . . . . , . . C4HaPcli . . . . . . . . . . . . . . . . . . . . . Lo-CtHaPClr . . . . . . . . . . . . . . . . . . .
(CrHdIAl (CaHT)a& (iao-CaHi)rAl (CIHa)rAI (iso-CtHv)rAl
n-CeHiaPClr ....................
(n-CtHdaAl
.....
83 80 77 73 86
PClt [(CIHI)YO] Pcll r(CYH1)101 PCla [(CrHdrO] PCla [(CIRaN) PCla [(CrHdfi or CiHrNl PCl:
24.6
140-141/S7 mm. 138-139/65 mm. 262-2S3 270 243-244
51 43 s7 36
112 1.93 130/745 mm. 38.69819 mm. 14&149/740 mm.
42
83-84/9 mm.
82
(342) (342) (342) (340, 342) (342) (342) (340, 342) (342) (342) (342)
CrHiPClr ......................
(CrH8)dPb
C I H I ~ ~ P C..................... I, CrHaPBra ......................
(CrHa)iPh (CzHihPb
1:
"PCla
3. From phosphorus trihalides
+ PCla
4
RCHClCH2PClr
The free radicals may be generated by the thermal decomposition of acetyl peroxide (155, L56) or azobisisobutyronitrile (366), by ultraviolet irradiation (157, 186), or by subjecting high-molecular-weight linear polymers to shear stresses (266). For effective propagation of the chain reaction, the group R should be aliphatic and the carbon atom to which it is attached should carry a hydrogen atom (156). Only two compounds have been prepared by this method. 2-Chlorooctylphosphonous dichloride, b.p. 85-88"C./0.5 mm., was obtained from 1-octene and phosphorus trichloride in 38 per cent yield (155, 156), m d 2-chloro-2- (3-cyclohexen-1-y1)ethylphosphonous dichloride, b.p. 99--102"C./l mm., was obtained from 4vinylcyclohexene and phosphorus trichloride in 17 per cent yield (186). For another reaction of olefins with phosphorus trichloride see Section II,A,2. (b) With diazo compounds At temperatures low enough to moderate the violence of the reaction (-50' to -60°C.), phosphorus trichloride reacts with diazoalkanes giving a-chloroalkylphosphonous dichlorides in 35-50 per cent yields (357, 359). RCHN.
+ PCla
4
RCHClPClt
113-116
99 78
161
(32. 84, 158, 159, 160, 264, 297) (306) (309)
prepared by this method are given in table 7.
(a) With olefins Phosphorus trichloride can be made to add to olefins under free-radical conditions. The products are 8chloroalkylphosphonous dichlorides: RCH=CHn
96
+ Nr
Equally satisfactory results are obtained with phosphorus tribromide (357, 359). Phosphonous dihalides
4. From elemental phosphorus with alkyl halides Elemental phosphorus reacts with alkyl halides a t elevated temperatures to give mixtures of organophosphorus compounds. If the conditions are suitable, primary phosphonous dihalides can be made the predominant products. The perfluoroalkyl iodides may be made to give the desired products simply by adjusting the proportions of the reagents (34, 49, 74) : CFsI
+P
+
CFaPIt
Rigorous exclusion of atmospheric contaminants is necessary if good yields are to be attained (49). When white phosphorus is used, iodine should be added as a catalyst (49). Red phosphorus reacts with alkyl halides in the presence of copper powder a t 28O44O0C.,giving phosphonous dihalides as the principal products (196). Small amounts of phosphinous halides and phosphorus trihalides are obtained as by-products. The phosphonous dihalides prepared by this method are listed in table 8. 6. From phosphonous acids
Although the phosphonous dichlorides may be considered to be acid chlorides of the phosphonous acids, few attempts have been made to prepare them by the usual methods. Phosphorus pentachloride gives the phosphonic dichloride, owing to oxidation (230, 240), but phosphorus trichloride gives the phosphonous dichloride (111). Only one reaction of this type is known. Prolonged refluxing of triphenylmethylphosphonous acid with phosphorus trichloride gave an unstated yield of triphenylmethylphosphonous dichloride, m.p. 138140°C., together with much phosphorous acid and free phosphorus (1 1 1).
TABLE 7 Phosphonous dihalides prepared from diazo compounds Preparation from Phosphonoua Dilialide
CICHaPCla . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . BrCHaPBrr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CHICHCIPCI~. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CallrCHCIPClz. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diazo compound
PX:
CHrNr CHtNr CHiCHNi CiHiCHNr
PClr PBra PClI PCll
Yield
Boiling Point
per cent 40 50 35
OC. 80-81/140 mm. 7014 mm. 03.&64.5/60 mm.
(3.57. 359) (357, 359) (357, 359) (357)
402
ARLEN W. FRANK
TABLE 8 Phosphonotir drhnlides prepared from elemental phosphorus with alkyl halidea Preparation from Phosphonous Dihalide
Yield Alkyl halide
Catalyst
CHaCl CHiBr CHaI CFiI CiHsBr CiFd
cu cu cu
Boiling Point
per cent
CHaPClr. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CHiPBrr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CHIP11. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CFiPIi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cr€IlPBr, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CiFIPIr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References
OC.
78 139.-.141 73-7tV.5 mm. 69/29 mm. 161 190
42
Cu 1s
6. From phosphonous diesters
9. From tetrahalophosphoranes
Treatment of phosphonous diesters with phosphorus trichloride a t 5°C. in ether solution gives phosphonous dichlorides in 50-60 per cent yield (305) :
Elemental phosphorus reduces alkyl- or aryltetrahalophosphoranes (RPXr) to the phosphonous dihalides (96, 97, 335):
RP(0R)i
+ PCls
4
RPClr
+ (R0)sPCl
If excess phosphorus trichloride is added, the by-product is an alkylphosphorodichloridite, ROPClg (305). The phosphonous dichlorides which have been prepared by this method are butylphosphonous dichloride, b.p. 60-65OC./17 mm., and phenylphosphonous dichloride, b.p. 82--85OC./5 mm., both prepared from the corresponding diethyl ester (305). Y . From phosphorobenzene and rebated compounds Treatment of phosphorobenzene (see Section 111,B13) with bromine in carbon tetrachloride gave phenylphosphonous dibromide, b.p. 132OC./14 mm., 93OC./2 mm., in quantitative yield (182, 183). (C6HsP)4
+ 4Br2
-+
4CtHsPBrl
A similar reaction with chlorine gave phenylphosphonous dichloride (169). Tetrakis(trifluoromethy1)cyclotetraphosphine, another compound with a PI ring structure, reacts with iodine a t room temperature giving a quantitative yield of trifluoromethylphosphonous diiodide, but chlorine gives only the tetrachlorophosphorane, CFaPCh (195). 8. From primary phosphines
Treatment with a halogen converts primary phosphines to the phosphonous dihalides (332). RPH, + 2 X *
-+
RPXi + 2 H X
The halogen is added gradually to a dilute solution of the phosphine at 2OOC. until a precipitate of the tetrahalophosphorane appears. Further addition would, of course, convert all of the dihalide to the tetrahalophosphorane. Butylphosphonous dibromide, b.p. 80-95OC./ 10 mm., was thus obtained in 44 per cent yield (332). Treatment of phenylphosphine with phosgene gives phenylphosphonous dichloride according to the following equation (242) : Cd&PHi
+ 2COClr
+
C&LPCb
+ 2CO + 2HC1
BRPCI,
+ 2P
3RPCli
4
+ 2PC4
Iodine may be added as a catalyst, but its presence is not essential (96). The tetrachlorophosphoranes are prepared by the addition of chlorine to phosphonous dichlorides or by the addition of phosphorus pentachloride to olefins. The latter reaction gives ,!l-chloroalkyltetrachlorophosphoranes, which when reduced lose the'elements of hydrogen chloride, giving a,p-unsaturated phosphonous dichlorides (335, 354) : 3RCHClCH2PCC
+ 2P 2
3RCH=CHPCls
+ 2PC1, + 3HCI
A new reducing agent, useful because it yields volatile by-products, is methylphosphorodichloridite (285), The reduction of methyltetrachlorophosphorane proceeds as follows: CHsPCl4
+ CHjOPClz
4
CHiPCll+ POCI:
+ CHGI
The complexes obtained in the Kinnear-Perren synthesis are complexes of aluminum chloride with tetrachlorophosphoranes. They may be reduced to the phosphonous dichlorides by elemental phosphorus (172, 327), aluminum (118, 172), or sodium (172). Freshly calcined potassium chloride is used to bind the aluminum chloride, except when sodium is used as the reducing agent, as the sodium chloride produced serves the same purpose (172). 3[RPCl,][AlCIJ
+ 2P + 3KC1
4
3RPCIf
+ 2PC1: + 3K2AICI4
The phosphonous dihalides prepared by these methods are given in table 9. 10. From other phosphonous dihalides
Phosphonous dibromides can be prepared by treatment of phosphonous dichlorides with dry hydrogen bromide a t the reflux temperature until no more is absorbed (246). RPCl,
+ 2HBr
4
RPBrs
+ 2HC1
THE PHOSPHONOUB ACIDS AND THEIR DERIVATIVES
403
TABLE 9 Phosphunous dihalides prepared from telrahalophosphoranes
I CHrPCI1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CHIPII......................................... CFrPClr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CClIPClY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CCIrPClr ....................................... C~HrpClr. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
I
Preparation from
I
Phosphonoua Dihalide
I
Tetrahalophosphorane
I
CHd'C14 CHiPIa CFrPCI4 CClrPCl4 CClrPC14 CsHsPCh
Reducing agent CHrOPClr P Hg OHrOPClr P, PI1 P
I
Yield
I
par cent
z;2
Boiling Point
00.
OC.
77 43 99 80 98
References
81-82 69-70/23 mm. 82-83/7 mm. 91-93/8 mm.
(285) (98) 1195) (285) (97) (335)
mm. 100-102/100 mm. 70-72/3 mm. 135-138/8 mm. 104-105/1 mm.
(335, 354) (354) (335, 354) (335, 354) (335)
81-82 mm. 87/20 113-114/752 mm.
(118, 172) (327) (172)
8&70/2 47 50-52
mm.
Olefin-PClr method CdHiPCIz. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CrH9PClr. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . GHirPClr.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C ~ H I C H S H P C I S. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . C9HiPCl:. ......................................
2-Methylpropene, PC1s I-Pentene, PCls Diisobutylene, PCls Styrene, PCls Indene, PCls
P P P P P
CHiPClr.. ...................................... CChPCh. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C I H ~ P C I .~... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
CHrCl, PCla, AlCIr CCh, PClr. MClr CgHsCl, PClr, AlClr
AI, KCl P P. KCl
The reactions are far from simple however, as benzene, bromobenaene, phosphorus, phosphorus trichloride, and phosphorus tribromide have been isolated as byproducts (246). A similar treatment of phosphonous dichlorides with hydrogen iodide at elevated temperatures yields the hydriodic acid salts of the phosphonous diiodides (96, 188, 230). These are dark-colored compounds which resemble iodine in appearance and which evolve hydrogen iodide on heating. Conversely, phosphonous dichlorides may be prepared from the diiodides (and probably also from the dibromides) by treatment with silver chloride (34, 74). According to Anderson (6), exchange reactions with other covalent halides occur whenever a more volatile component can be distilled from the reaction medium. Thus, phenylphosphonous dichloride reacts with silicon and germanium tetrabromides to give phenylphosphonous dibromide, and with propyltriiodosilane to give phenylphosphonous diiodide (6). 2CeH'PClg 3C8HtPC4
+ GeBr,
+ 2CaH&liI*
+ GeCl, 3CsH,PI* + 2C8HtSiCl,
+ ZCeHJ'Br, -+
88
98-104/100
85 54
28
1 hi 1 1 40
~~~
The same principle is used in exchanging chloride groups for isocyanate and isothiocyanate groups (see Section 111,B14). The phosphonous dihalides that have been prepared by these methods are listed in table 10. 11, F r m higher organophosphorus compounds
N o method has yet been devised for converting secondary or tertiary phosphorus compounds to primary phosphonous dichlorides. The thermal decomposition of tertiary phosphine dihalides (RaPX2) gives secondary phosphinous halides (RZPX) with the elimination of alkyl halide, but attempts to extend this reaction to the synthesis of primary phosphonous dihalides have not been successful. Likewise, attempts to induce trivinylphosphine or dibutyldivinyltin to undergo redistribution reactions with phosphorus trichloride gave only black solids, despite the success of these reactions with arsenic and antimony analogs (140). B. REACTIONS OF PHOSPHONOUS DIHALIDEB
The reactions of phosphonous dihalides which yield derivatives described in detail in other sections of this
TABLE 10 Phosphonous dihalides prepared by halogen exchange Preparation from Phosphonous Dihalide
CHIPI:. H I . ............... CFrPClt ................... CrFiPClr. .................. CrHrPBr: .................. CIHIPI:. H I . . ..............
Phosphonous dihalide CHrPClr CFiPI: CrFiPIr CtHsPClt CsHrPClr
I
I
1
Melting Point
Boiling Point
OC.
OC.
Reagent psr cent 75 82 98
85-87 37 88.4 255-257
Referencea
(98) (34, 195) (74) (246) (188. 230)
404
ARLEN W. FRANK
review are not considered here. These include hydrolysis to phosphonous acids (Section TI,A,4); est>rrification to phosphonous monoesters (Section VIII,A,2), tto phosphonous diesters (Section IV,A,B), to phosphonochloridous esters (Section VI1,A) or to phosphonodithious esters (Section V,A) ; amidation to phosphonous diamides or iminophosphines (Section V1,A) or to phosphonamidous chlorides (Section VI1,B) ; synthesis of mixed anhydrides with dialkyl phosphites (Section X,A,1) or with phosphonous monoesters (Section X,A,2); and exchange reactions with other halides to form different phosphonous dihalides (Section III,A,lO). 1. Scission of the cnrbon-phosphorus bond
A few phosphonous dichlorides have been observed to undergo scission of the carbon-phosphorus bond under conditions where most such compounds are stable. Phosphonous dichlorides which contain strongly electronegative substituents on the carbon atom attached to the phosphorus atom are the most susceptible. Trichloromethylphosphonous dichloride, for example, suffers scission of the carbon-phosphorus bond on treatment with oxygen-free boiling water (97) : CChPCla
+ 3H20
-+
CHCls
+ HJPOI + 2HC1
Triphenylmethylphosphonous dichloride, (C6Hs)3CPCI,, undergoes cleavage when subjected to the oxidizing treatments usually employed to convert phosphonous dichlorides to phosphonic acids, such as chlorination and hydrolysis or chlorination and treatment with sulfur dioxide (1 11). The same result is obtained on shaking with iodine and sodium bicarbonate (111). Another class of sensitive compounds comprises the p-dialkylaminophenylphosphonous dichlorides (252). The p-dimethylamino derivative in dry ether absorbs anhydrous hydrogen chloride, giving a white precipitate which redissolves and then deposits dimethylaniline hydrochloride : p-(CHt)zNCsHdPClr
+ 2HCl -,
(CHa),NCsHa.HCl
+ PC1.q
The chlorination of methylphosphonous dichloride in concentrated solution or a t temperatures above 40°C. is accompanied by some cleavage of the carbon-phosphorus bond (285). 2. Reduction
Phosphonous dihalides may be reduced to primary phosphines with lithium aluminum hydride (35, 123, 124, 182, 183, 268, 299, 339). Tf an excess of the dihalide A i present in the reaction mixture, as it usually is, the yield of phosphine cannot be greater than 50 per cent because the product reacts with the starting material forming a compound with a phosphorus-phosphorus bond. Phenylphosphonous dichloride, for example, forms “phosphorobenzene” (see Section III,B,3). Sub-
sequent aqueous treatment of the reaction mixture to decompose the hydride convert>sthe phosphorobenzene to equal parts of phenylphosphine and phenylphonphonic acid (123). Phenylphosphonous dichloride can also be reduced to phenylphosphine by lithium hydride (123), by sodium hydride (123, and by a finely divided dispersion of sodium in toluene followed by water (122, 123,268). Potassium borohydride is said to be unreactive (123), but lithium borohydride reduces phenylphosphonous dichloride to a crystalline borine adduct, CaHaPHa.BHI (847). A deficiency of the reducing agent in the latter reaction yields an unstable adduct, CBH~PHCI. BHs, which gradually loses hydrogen chloride and hydrogen forming a high-molecular-weight polymer, (CaHaPBH), (347). Other reducing agents have been tried without success (35, 228, 230). Some yielded traces of phenylphosphine, detected by its odor. Two-step reduction via the phosphonous acid is discussed in Section II,B,l. 3. Phosphorobenxene and related compounds
Phosphorobenzene, as described in the preceding section, is bbtained when phenylphosphonous dichloride is reduced with lithium aluminum hydride (123,268,299). It may also be prepared by the reaction of equal parts of phenylphosphine and phenylphosphonous dichloride in ether solution (169, 182, 183, 268,339). Theproductisa colorless, crystalline compound, m.p. 14S-15OoC. Most texts give its structure as a dimer (I), but mcasurements of the molecular weight of phosphorobenzcrie in numerous solvents show that it is actually a tetramer, (c6HaP)4. Recent investigat>orshave suggested that it contains a cyclic structure (11) and have renamed it tetraphenylcyclotetraphosphine (182, 183, 195, 268). CsHnP-PCsHs CeHsP=PC.& I
I I
CaHsP-PCsIIs
I1
In addition to this compound, which melts a t 149150”C., higher-melting solids have been isolated, melting a t 171°C. (339) and 188-192°C. (299). The structural relationship of these compounds to the cyclic tetramer has not been definitely established, but they appear to be oligomers of higher molecular weight (299). Otther aromatic compounds related to phosphorobenzene have also been prepared. The product from p chlorophenylphosphine and p-chlorophenylphosphonous dichloride was found to be resinous (234). The condensation of phenylphosphonous dichloride with phenylarsine gives a phosphoarsenobenzene, designated as C&IsP=AsCeHs (322), which easily undergoes dismutation to arsenobenzene and phosphorobenzene, even on recrystallization from benzene. The only other four-membered cyclic organophos-
405
THE PHOSPHONOUS ACIDS AND THEIR DERIVATIVES
phorus compound to have been investigated in detail is tetrakis (trifluoromethyl) cyclotetraphosphine, m.p. 66.3-66.4"C., b.p. 145" (48, 195). This compound is prepared by shaking trifluoromethylphosphonous diiodide with a large volume of mercury a t room temperature. QCFSPI,
+ 4Hg
-+
(CFsP),
+ 4HgIa
In addition to the tetramer a cyclic pentamer, m.p. -33"C., b.p. 19O"C.,is produced in this reaction (195). Several reactions are recorded in the early literature on organophosphorus chemistry which gave ill-defined products apparently related to those described above. The reaction of phenylphosphonous dichloride with phosphine gave hydrogen chloride and a yellow viscous solution which was believed to contain the following product (229) : CsHsPClp
+ PHs
-+
CsHsP=PH
+ 2HC1
The structure of the product follows from its oxidation with nitric acid to give phenylphosphonic acid and phosphoric acid. Similar substances are apparently formed by the action of moisture on phenylphosphonous dichloride (99, 253). The reaction of phenylphosphonous dichloride with one mole of water commences a t lOO"C., with the copious evolution of hydrogen chloride, and is complete at 260°C. On cooling there is obtained a bright yellow mass from which phenylphosphonous acid, phenylphosphonic acid, and diphenylphosphinic acid are extracted with water. The residue contains the yellow compounds CaHbP4H and CaHsP4H * CeH6P02, separated by their difference in solubility in carbon disulfide. The compound C6HsP4Hyields the same products on chlorination or oxidation as would be expected from the compound CeH5P=PH (99). The same results are obtained in the reaction of phenylphosphonous dichloride with phenyiphosphonous acid (99). Larger amounts of water, of course, hydrolyze phosphonous dichlorides to the corresponding acids (see Section 111A14). Phenylphosphonous dichloride reacts with hydrogen sulfide when heated near its boiling point, evolving hydrogen chloride (170). The phosphonous dichloride is believed to suffer initially a dismutation, since the sulfur-containing products yield diphenylphosphinic acid and not phenylphosphonic acid on oxidation.
4. Reaction with pseudohalogen compounds Phosphonous dihalides react with silver cyanide (234), silver cyanate (112, 113, 196), and silver thiocyanate (234), giving products with properties similar to those of the phosphonous dihalides themselves. The preparation of phenylphosphonous diisothiocyanate is given as an example: CeHsPCln
+ 2AgSCN
4
C*HsP(NCS)1
+ 2AgCI
These compounds can also be prepared by exchange
reactions with other covalent isocyanates or isothiocyanates, if conditions are such that, the halide which is produced in the exchange can be'distilled from the reaction mixture (6) : CsHaPC12
+ (CzHs)aSi(NCS)2
CaHsP(NCS),
-+
+ (CzHs)2SiCh
The dicyanides, RP(CN)Z, are stable to water but are hydrolyzed by dilute sodium hydroxide solution to sodium cyanide and the sodium salt of the phosphonous acid (234). They form adducts with chlorine, but subsequent treatment with sulfur dioxide gives no homogeneous product. The diisothiocyanates are decomposed by water and give organophosphorus tetrachlorides with chlorine (234) : RP(NCS)z
+ 3c12
RPC14
-+
+ & + 2ClCN
The diisocyariates form the expected urethan and urea derivatives with alcohols and amines (112, 113). 5. Addition of oxygen, sulfur, or selenium As compounds of trivalent phosphorus, the phosphonous halides are capable of adding oxygen (97, 11 l), sulfur (19, 22, 80, 104, 118, 131,168, 196,267, 297,335), or selenium (196) to form the corresponding phosphonic, ,phosphonothionic, or phosphonoselenonic dihaliaes. The direct oxidation of phosphonous dihalides is seldom if ever used as a preparative method, but the addition of siilfur is well known. A catalyst such as aluminum chloride is required (19, 131); in its absence, sulfur is precipitated unchanged even after heating to 114°C. (19). At higher temperatures phosphonous dichlorides and siilfur react with violence (168). RPCla
+8
AlCls -+
RP(S)Clp
For best results, the sulfur should be added to a mixture of the phosphonous dichloride and aluminum chloride (1 18). Thiophosphoryl chloride (100, 131) or phos-' phorus pentasulfide (131) may be used in place of elemental sulfur. 6. Addition of halogens Phosphonous dichlorides react vigorously with chlorine giving yellow crystalline adducts resembling phosphorus pen tachloride in appearance (64, 92, 104, 190, RPCI,
+ Clz
-+
RPClr
191, 192, 195, 223, 225, 227, 230, 233, 234, 235, 236, 238, 250, 251, 252, 265, 304, 343, 344, 348, 355, 357). Adducts with bromine have also been prepared (186, 194 230, 234, 246). Methylphosphonous dichloride, CHaPCIz, absorbs more than the theoretical amount of halogen, owing to halogenation of the alkyl group (285, 358, 366). The intermediates can be isolated if the calculated amount of halogen is used. Chlorination of the aromatic ring in arylphosphonous dichlorides has also been observed (33 1).
406
ARLEN W. FRANK
If phosphorus pentoxide is present in the slurry during halogenation, the product is converted to a phosphonic dichloride (326). Sulfuryl chloride also oxidizes phosphonous dichlorides to phosphonic dichlorides (264, 306). Sulfur monochloride, however, produces a mixture of phosphonothionic dichloride and tetrachlorophosphorane in 2: 1 ratio (131, 165, 198) : 3RPClz
+ &Clr
-+
2RP(S)Cb
+ RPCI,
Phosphonous dichlorides undergo a redox reaction with antimony pentachloride (167). The products are complexes : RPCls
+ 2SbCls
+
RPC14.SbCls
+ SbCli
pounds (32) , organozinc compounds (338), or organomercury compounds (63, 109, 206, 224, 231, 238, 248, 274, 287, 337) : Ce.”sPClt
+ &Hg
-+
CsHsRPCl
+ RHgCl
An attempt to use an organolithium reagent failed because even when the lithium compound was added slowly to a large excess of the phosphonous dichloride in ether solution, the only products were the tertiary phosphine and unreacted dichloride (109). Phosphinous halides are also obtained, albeit in low yield, when phosphonous dihalides are heated for prolonged periods a t 300°C. (17, 34, 43, 69, 74, 94). This method has been used with phenylphosphonous dichloride and two fluoroalkylphosphonous diiodides (RPL: R = CFs or C,F,), but does not work with the tolyl or higher aryl homologs (238).
No reaction is observed with silicon tetrachloride, zinc chloride, or titanium tetrachloride (167). Antimony pentafluoride gives the tetrafluorophosphorane (318), replacement of the chlorine atoms occurring simultaneously with the redox reaction. The same results are achieved with a mixture of phosphorus pentachloride and antimony trifluoride (318).
In these reactions the trivalency of the phosphorus atom is preserved.
7. Other addition reactions
(b) Secondary phosphinic compounds
Methylphosphonous dihalides react with metallic nickel under mild conditions giving complexes such as Ni(CHaPClz)4 in high yield (196, 284). Phenylphosphonous dichloride does not react with nickel under the same conditions, but the complex Ni(C~H~PCl~)* can be made by the reaction of phenylphosphonous dichloride with nickel carbonyl (199) or by an exchange reaction with tetrakis(dichloromethy1phosphine)nickel (284). Cobalt carbonyl gave a product which could not be characterized (303). Phenylphosphonous dichloride reacts with the sodium salts of chloroamidesof aromatic sulfonic acids, forming dichlorophenylphosphazosulfonaryls(314) :
The use of a phosphonous dihalide as the phosphorus component in several well-known reactions of phosphorus trichloride gives rise to compounds with one new carbon-phosphorus bond. In the Kinnear-Perren reaction, a crystalline ternary complex is formed from a phosphonous dichloride, aluminum chloride, and an alkyl halide, and is then decomposed by the addition of enough water to break up the complex (37, 126, 162) :
CeHsPC12
+ ArS02NNaC1
+
C&P(=NSO,Ar)Clr
+ NaCl
The same products can be prepared by the reaction of CsH6PC14with aromatic sulfonamides (314). Phenylphosphonous dichloride forms an equimolecular adduct, m.p. lO”C., with dimethylphenylphosphine (169), the identity of which has not been clearly established. 8. Candensations in which me new carbon-phosphorus bond is formed Phosphonous dihalides take part in condensation reactions with replacement of one or both of the halogen atoms. The former will be discussed first.
(a) Phosphinous Compounds Phosphinous halides are of ten by-products of the synthesis of phosphonous dihalides. With the use of more severe reaction conditions it is possible to convert phosphonous dichlorides to phosphinous chlorides in good yield, as in the reaction with organolead com-
2CsHbPC1, + (CsHs)zPCl
RPClr
+ AlC1, + R’C1
-+
+ PC&
[RR’PClr][AIClr]
RR’P(0)Cl
If the complex is decomposed with sulfur or a sulfide (of aluminum, phosphorus, arsenic, or antimony) instead of water, the product is a phosphinothionic chloride (126). In the oxidative phosphonation method, gaseous oxygen is passed into a solution of a phosphonous dihalide in an aliphatic hydrocarbon such as cyclohexane until no more heat is evolved (319, 367) : 2RPCls
+ 0s + CsHir
RCaEiiiP(0)Cl
+ RP(O)Cl, + HCl
If the aliphatic hydrocarbon is an unsaturated one, such as propylene, the product will contain a chloroalkyl group (367). In the diazonium fluoborate method, a phosphonous dihalide is treated with an aromatic diazonium fluoborate in the presence of cuprous bromide (83, 85, 87, 88) : RPClt
+ R’NtBF4
CurBrt
+ RR’P(0)OH
Unlike the products obtained in reactions of diazonium fluoborates with phosphorus trichloride, the secondary phosphinic acids are not contaminated with higher condensation products; no tertiary phosphine oxides
407
THE PHOSPHONOUS ACIDS AND THEIR DERIVATIVES
are produced (83). The yields are somewhat low, however, owing to difficulties in removing small amounts of symmetrical secondary phosphinic acids which arise from redistribution reactions (83). Equally good results are obtained with diazonium fluosilicates (85). The fluosilicates have the advantage of being more stable and easy to isolate than the fluoborates, and react with less violence (85). Phosphonous dihalides react with aldehydes under mild conditions, giving a-hydroxyalkylphosphinates (234). RPClr
+ CH‘CHO
R(CH~CHOH)P(O)OH
4
This reaction takes a different course in the presence of a tertiary nitrogen base. The product is a vinyl ester of a phosphonic acid, probably resulting from the formation and dehydrohalogenation of an intermediate a-chloroethyl ester (93, 271). No new carbon-phosphorus bond is formed. RPClr
+ CHaCHO %
RP(O)(OCH=CH&
At higher temperatures phosphonous dichlorides react with aldehydes, giving a-chloroalkylphosphinates (137). RPCl,
+ HCHO
+
R( CICHt)P(0)Cl
Phosphonous dihalides react with a,&unsaturated ketones giving cyclic adducts which yield y-ketophosphinic acids on hydrolysis (55). If acetic anhydride is added to the reaction mixture, the intermediate is a cyclic anhydride (55,70). CaHsPClr
+ C~H&H=CHCOCBH~ (C€IICO)Yo
JI. II
CbEi
Glacial acetic acid gives the y-ketophosphinic acid directly (54). 9. Condensations in which two new carbonlphosphorus bonds are formed
Of the reactions which proceed with replacement of both the halogen atoms in phosphonous dihalides, the best known is.the reaction with Grignard reagents (29, 30, 53, 59, 60, 61, 62, 63, 64, 65, 67, 89, 94, 102, 103, 125, 128, 129, 130, 132, 134, 140, 141, 148, 196, 197,201, 203, 205, 206, 224, 274, 288). A typical example is the following (201) :
+ 2CzHsMgI
-+
(CzHi)zPCd&
+ RIZn
R‘&P
+ ZnCll
In one instance the use of metallic ainc with an alkyl halide was recorded (244). The product was actually the tertiary phosphine oxide (203) and probably arose from oxidation during the reaction or later. The organozinc compounds have been superseded by the Grignard reagents. Tertiary phosphines may also be prepared with organolithium compounds (95, 109, 187). The novel heterocyclic compound “pentaphenylphosphole” was prepared by this method, using a dilithium compound derived from diphenylacetylene (187). The phosphole was also prepared from the iron tricarbonyl derivative of diphenylacetylene (42). Phosphonous dihalides react with alkyl or aryl halides in the presence of sodium, forming tertiary phosphines (69, 120, 121, 200, 203, 238, 243, 252, 307, 313). This reaction has been used to synthesize several five- and six-membered heterocyclic phosphorus compounds. Ethyl acetate is added as a catalyst (120, 203). The yields are much poorer than the yields of the corresponding arsenic analogs (49, 121), probably because of formation of quaternary salt with the excess alkyl halide (122). The reaction of chloromethylphosphonous dichloride with diazomethane does not give secondary or tertiary phosphines (97). Instead, there is obtained a homogeneous, amorphous substance with the empirical composition C4H8PnCla02. One possible formula for this substance is the following (97): (CICHs)rPCHxP(0)(CH&I)OH
___)
CbEi&HCH=CCbEi~
CsHIPCli
R’PCI,
+ 2MgClI
Secondary alkyl bromides do not give the expected products (67) unless the Grignard reagent is used in large excess (59). The use of organozinc compounds is commonly found in the older literature (56, 58, 153, 230, 234, 235, 236, 23a,24o124i, 252,304) :
Phosphonous dihalides react with a wide variety of Diels-Alder type dienes, giving 1-substituted l-phospha-3-cyclopentene P,P-dihalides, which are readily converted to the phosphine oxides by hydrolysis (221). A typical example is the reaction of phenylphosphonous dichloride with isoprene (221) : CeHsPClp
+ CH&HC=CH*
+
I=IcHs
An inhibitor is added to prevent polymerization of the dime (221). The initially formed dichloride may also tw converted to the phosphine sulfide by treatment with hydrogen sulfide (222), or to the phospholene by reduction with lithium aluminum hydride (29). IV. PHOSPHONOUS DIESTERS ‘l’he phosphonous diesters are colorless liquids with characteristic unpleasant odors. They are easily oxidized and nrc be& handled in an inert atmosphere. The lower alkyl members burst into flame when poured onto filter paper (19).
408
ARLEN W.
A. SYNTHESIS OF PHOSPHONOUS DIESTERS
1. From phosphorochlom’dites (a) With Grignard reagents Dialkyl (138, 305) and diary1 (146, 305) phosphorochloridites react with Grignard reagents, giving phosphonous diesters in 45-70 per cent yields. Trialkyl phosphites are unexplained by-products (305). (R0)rPCl
+ R’MgCI
4
R’P(0R)r
+ MgCli
If the reaction is run at a low temperature] the chlorine atom is selectively replaced without contamination by alkoxy group substitution (138). Buch contamination may account for the differences in physical properties observed (19) between ester$ prepared by this method and those prepared by the phosphonous dichloride/ alcohol/amine method described in the following section. Other organometallic compounds have been used in place of Grignard reagents, but they have not been a8 successful. Cadmium alkyls give lower yields, and lithium alkyls attack the alkoxy groups as well as the halogen (305). A list of the phosphonous diesters prepared by this method is given in table 11. (b) With alkyl halides and sodium Phosphonous diesters, especially the aromatic diesters, mav 5e prepared by the reaction of phosphorochloridites with alkyl halides in the presence of sodium (75). (RO)rPCl
+ R’Cl + 2Na
-+
R’P(OR)*
+ 2NaCI
The reaction is carried out in a finely divided dispersion
FRANK
of sodium in xylene a t 260-280°C. (75). The patent in which this renction is described does not describe the products in detail. They were produced by the reaction of diarylphosphorochloridites with chlorinated esters of abietic acid and may have contained other by-products such as the products of self-coupling of the halides. 1. F
T O trialkul ~ phosphites with Grigncsrd reagent8
Under cnrefully controlled conditions Grignard reagents react with trialkyl phosphites to give phosphonous diesters, together with small amounts of the unreacted phosphite (305) : (RO)sP
+ R’MgX
4
R’P(OR)*
+ Mg( 0R)X
More shingent reaction conditions yield higher substitution products (193, 305). The temperature a t which reaction takes place depends on the Grignard reagent. This method is more convenient to use than the reaction of Grignard reagents with phosphorochloridi tes, because the phosphorochloridites are more difficult to obtain in a pure state (305). The reaction of tributyl phosphite with butylmagnesium chloride gave dibutyl butylphosphonite, b.p. 109112”C./13 mm., in 69 per cent yield (305). Other phosphonous diesters have been prepared by the reaction of trimethyl phosphite with ethylmagnesium chloride, butylmagnesium bromide, benzylmngnesium chloride, and phenylmagnesium chloride in 30-54 per cent yields (193, 305).
3 From phosphonous dichlorides Phosphonous diesters may also be prepared by the reaction of a phosphonous dihalide with (a) an alkoxide or (b) an alcohol in the presence of a tertiary amine. In the
TABLE 11 Phosphonotia diesters prepared lrom phosphmochloridites Prepsrst,ion from Phosphonous Diester
CHrP(OCtH,)r . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CHrP(0CeHdr. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CI&P(OC:H~):. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CrHrP(0CtHr)r. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . GrItP(OC4Hdr.. . . .............. CrHrP(OCsH,)i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CrHiP(OC4He)r. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.. I_)P(OC4He)r.
..........................
Phosphoroahloridite
Urignard reagent CHrMgCI CHiMgI CiHrMgCl CrHsMgC1 CIHEMKC~ CtHlMgBr CrHiMgCl iso-CaH7MgBr CiHeMgCl C~HOMRCI CcHeMgBr
Yield
par csnl 70 45 57 84 70 87 70 63 88
r> M & l
Boiling Point
0
c.
38-40/1 mm. 212-213/10 mm. 53/30 mm. 66-56.5/7 mm. 47-48/1 mm. 223-225/11 mm. 59.8-60.3/1 mm. 212-214/11 mm. 78/20 mm. 68-89/1 mm. 225-226/8 mm. 81.5-83/2
mm.
_ .
CeHuP(OCsH,)r . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CeHrCHrP(0CtHr)r. . . . . . . . . . . . . . . . . . . . . . . . . . . CIILCH~P(OC~H~)~ .................. COHIP(OC:H~)~. .......................... CeHrP(0CcHeh. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CrHrP(0CeHsh. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-CIPHIP(OC~HI)Z. ...........................
CsHllMgBr CaHsCH2MgCI CsHrCHiMgCl CsILMgCl CsHrMgCl CaHsMgCl CeILMgBr 1-CroHlMgBr
49 50 54 63 62 63 75
233-235/10 mm. 88-g0/3 mm. 103-101/1 mm. 100/5 mm. 73-74/1 mm. 97.5-98.5/1 mm. 223-224/10 mm. 245-247/10 mm.
Referencea
409
THE PHOSPHONOUS ACIDS AND THEIR DERIVATIVES
older alkoxide method, t8he phosphonous dihalide is added to a dry alkoxide under ether (9, 251) : RPCln + 2R'ONa
-+
RP(OR'),
+ 2NaCl
The alcohol/tertiary amine method is now preferred. The amine is added as an acid acceptor; in its absence the phosphonous diester is converted to the monoester with the loss of one mole of alkyl halide (see Section VIII,A,2). The tertiary amines most commonly used have been pyridine, dimethylaniline, diethylaniline, and triethylamine. Diethylaniline has an advantage in forming an easily filtered, nonhygroscopic hydrochloride (77). Other amines such as anhydrous ammonia may be used if they are added a t a rate just sufficient to neutralize the hydrogen chloride as it is formed (108). The esterification is usually run in ether solution at room temperature or below, and in an inert>atmosphere, as the products are easily oxidized. RPClZ
+ 2R'OH + 2 amine
-+
RP(0R')z
+ 2 amine.HC1
The tertiary amine can be omitted in the esterification of phosphonous dichlorides with phenols, as the aromatic esters are not attacked by acids (15, 220), and in the esterification of phosphonous dichlorides with oxiranes, as no hydrogen chloride is liberated (270). The phosphonous diesters that have been prepared by these methods are listed in table 12.
4. From other phosphonous diesters Treatment of a phosphonous diester with an alcohol results in a random redistribution reaction giving a mixture of esters, the proportions depending on the original ratio of diester to alcohol (117). For example, the transesterification of diethyl methylphosphonite (one mole) with n-octyl alcohol (three moles) gives on careful fractionation one mole of the diethyl ester, one mole of the ethyl n-octyl ester, and one mole of the di-n-octyl ester (117) : CHsP(OC2Hb)n
+ CHsP(0CsHirn)Z
e 2CHaP( OC&)( OCaHirn)
A list of the phosphonous diesters that have been prepared by this method is given in table 13. These phosphonous diesters, unlike the corresponding trialkyl phosphites, require no sodium catalyst for transesterification (115). B. REACTIONS OF PHOSPHONOUS DIESTER8
The reactions of phosphonous diesters which yield derivatives of phosphonous acids described in detail in other sections of this review are not considered here. These include the hydrolysis to phosphonous acids (Section II,A,5) or to phosphonous monoesters (Section IT,A,5; Section VIII,A,3) ; the reaction with phosphonous acids to form phosphonous monoesters (Section VIII,A,4) ; the reaction with phosphorus trichloride giving phosphonous dichlorides (Section III,A,6); and
the traiisesterification with alcohols to form other phosphonous diesters (Section IV,A,4). The phosphonous diesters undergo most of the reactions known for the trialkyl phosphites. Moreover, the reactions usually occur more readily and under milder conditions. The order of reactivity increases as follows (297) : (RO),P < RT(OR)?
< R:POR < R ~ P
Aromatic phosphonites are, of course, less reactive than aliphatic phosphonites, for the presence of the aromatic ring decreases the availability of the unshared electrons on the phosphorus atom (297). 1. Reduction
The reduction of diethyl phenylphosphonite with lithium aluminum hydride gives phenylphosphine in 62 per cent, yield (305). 2. Addition of oxygen, sulfur, or selenium
Phosphonous diesters, especially the lower alkyl members, readily add oxygen (21, 147, 295, 296, 297), sulfur (19, 21, 104, 115, 116, 138, 220, 270, 295, 297, 298), or selenium (295, 297), giving the corresponding phosphonic esters. NO catalyst is required. The products of oxidation have seldom been characterized, as they are more easily synthesized by other methods. Oxidants other than atmospheric oxygen have not been described. The addition of sulfur to phosphonous diesters gives phosphonothionates in 70-80 per cent yields according to the following equation : R'P(0R)t
+S
-+
R'P(S)(OR),
The phosphonothionic diesters are fuming liquids of characteristic unpleasant odor (19, 297). The ethyl esters, however, possess a pleasant and refreshing grassy odor (295). The selenium adducts of phosphonous diesters are refractive liquids of weak odor; they deposit selenium on standing in the air but can be stored indefinitely under carbon dioxide (295). 3. Other addition reactions
Phosphonous diesters, in common with other trivalent phosphorus compounds, react with copper monohalides to give adducts which are usually crystalline (9, 15, 19, 21, 138, 146, 147, 161, 295, 297). These adducts are often used for the characterization of the esters. The reaction of diethyl ethylphosphonite with phenyl azide gives N-phenyl 0,O-diethyl ethylphosphonimidate (135) : CJM"OC2Hs)z
+ CeJ3HsNs
+
CzHsP(=NCsHs)(OC*Hc)z
+ Nl
With carbon disulfide the phosphonous diestere form deep red solutions and differ therefore from the tertiary phosphines, which form crystalline adducts with car-
ARLEN W. FRANK
TABLE
12
Phoaphdturw dicelets prepared from p h o ~ ~ ~ h a ndichlarides ow ~
~~
Preparation from Phoiphonour Diater
Phorphonour d icIdod d e
. ........ CtHiPCL ................ CiHiPCh ............. CoHIPCt . . . . . . .. CCHiC&PCh . . . 2,4,6(CHdiC1HrPClr ~,~.~(C€II)ICIH~P(OCI&)~. . . . . 2,4,6(CHd1CiHrPClr ~-(CHI)SNCIH~P(OCH . ..I ~... . . C(CHr)rNCiBtPClc
CtH,P(OCHi)i . .... CI&P(OCIHI)S CIHIP(OCIH&O)I ~-CHICIH~P(OCIHJ)I.. . ~,~.~(CHI)ICIH~P(OC~HI)I. .
.. . . . . . .. , , . . . . . .. . . . . . . . . . . . . ... . . . . . . . . . . . . . . . . .. . . . . .. . . . . . . . . . . CSHIP(OCIHI)~.. .. CrEtP(OCiHriso)~.. . . . . . . . . . . CrHiP(OCHrCS!H)r. . . . . . . . . Ci%P(OCdHdr. . . . . . . . . . . . . . . CrHIP(OCiHi3r.. . . . . . . . . . . . . C ~ H I P ( O C O H.I.~. .
Yield
Mdtk Point
PI? sml
ec.
Alkoxide or aloohol
CHiONs CiHiONs iso-CtHiONa CrHiONa CrHiONs CIHION~ CHiONs
280
119 46
CHiPClr CHiPCl: CHiPCh CrILPClr CIHIPCII
CiHiOH CiHiOH iso-CiHiOH CHiOH CtHiOH
8a 78 80 35
CiHiOH iso-CIH,OH CHsCHCHnOH CH3CCHrOH CtHnOH CiHiiOII n-CtHuOH n-fhIIiiOH CaHtCHrOH CiHiOH Cr&OH CaHiOH CH~CCHIOH iso-CiHIOH CiHiOH CiHiOH CHF=CHCH~OH CHSCCHrOH CcHoOH iso-CtIIoOH CrH5OII CHIOH
64 40
CaHJP(0CIHidr. . . CrHIP(0CHrCIHI)r C ~ H ~ P ( O C I H I ) ~ ... CiHiP(0CrHi)r~ CHvP(0CiHi)r. . . CiHiP(0CHrWH)r iao-CIHiP(OCiHi-ilo)r. CdHrP(0CrHdr. .
CrHiPClr ClHIPCh CIHSPCL CrItPClr CrHfiPCL CIItPCll CrHiPClr CrHiPClr CrHiPClr CrHtPClr CIH~PCL CiHiPCh CiHiPClr iso-CiHiPClr C4HoPClr CtHoPClr CtHoPCh CtHd'Clr CdHsPClr Iro-CdHoPCh CsHiiPClr CtHiPClr
I
....*......
. . . . . . .. . .. . CIHIPCI~ . . . . .. . . . . . CIHIPCIS . . . . . . CiHiPCh n CIHIP(OCH~CHCHSO)S.. . . . . . C#&PCh CIHIP(OC:IIP~OO)S... . . . . . . . . CoHiPCl: CIHIP(OC~HVLSO)S. .. . . . . . . . . . CsHiPClr CtHiPClr CiH1P(0CsHidr. . . . . . . . . . . . . c HIP cII Ct€i~P(OCHrCtft)r.. . . . . . . . . CiHIP(OC#Hi)r.. . . . . . . . . . . . . . COHIPCL CIHIP(OCOH~CH~O)I. ... .. . . .. CoHIPClr CIrtP[OCsH4N(CHi)rmla. . . . . CIHIPCL Cc~~~tpc'h CCIC~HcP(OCH&B=CEr. . . CCHICOH~P(OCHI)~. . I . . . . . . . 4-CHiCoHtPCh ~-CHICIHIP(OCIHI)S.. .. . . .. . . P C H I C I H ~ P C ~ I CCHiCd%PClr CCHiC~HiP(0CrHI)r... ~-CHICIH~P(OC~H . .~.).I. . . . CCHtCiHtPClr CCHICIH~P(OCIH~~O . .O. .).~.. CCHiCsHtPCh CCH1OCtHtPCh CCEIrOCaHtP(OC:&)r. . . . . . . . ~ - C I O H I P ( O C H I ).~..... . , . . . . . 1-CioH~PCIr CIHIP(OC~HI)I. . . CtHiP(0CaHi)r. . . Ct&P(OCHrCH=CH:)r.
I
CIHIOH CIHIOH CHr-CHCHrOH Olycidol iao-CrHIOH iso-CdHsOH CaHirOH CIHICHIOH CaHiOH O-CHICIHIOH *(CHI)INCIH~OH CHFCHCHrOH CHIOH CiBOH CiHrOH CIH~OH bo-CtH10H CiHrOH CHIOH
66
80 91 90
711 64 74 60 64
70 64
64
85 31 70 81 75 43
232-233/100 mm. 283 (d.)/40 mm. 119-120/0.8 mm.
47/50 mm. 76/33 mm. 55/36 mm. 73.6-74.5/225 mm. 60/36 mm. 6666.5/11 mm. 73.5-74.5/36 mm. 86-87/11 mm. 126-127/6 mm. 63-64/3 mm. 81-82/2 mm. ~lOO-l01/2 mm. 142-144/3 mm. 14O-141/1.5 mm. 116-115.5/1 mm. 52-53/12 mm. 81-82/11 mm. 136-136.5/6 mm. 59.660.5/14 mm. 68-70/12 mm. 99.&101/14 mm. 98-lOO/ll mm. 146-147/6 mm. 116.5418.6/10 mm. 105.5-107.5/12.5 mm. 5860/0.12 m m . 94.5/13 mm. 70/0.5 mm.
137/16 mm. lOO/O. 3 mm. 99/0.6 mm.
60 77 45 74 45 4a
121-122/10 mm. l04/0.8 mm. 123-126/0.3 mm. 65-70/0.1 mm. 230/14 mm. 229-231/10 mm.
56
126-127/3 mm. 107-108/14 mm. 123-135/9 mm. 129-130/6 mm. 170-171/13 mm. 155-156/13 mm. 13&-138/13 mm. 101/0.15 mm.
51 €4
8a 09
77 _ I
AIcohol/no said soceptor method
........ .........,...... ............ ........... ..
CHIP(OCHICHCICHI)S Q&P(OCHrCHCLCH:h ........ Q&P(OCt&): Q&P(OCIH4CT-P)* Q&P(OGH4CHro)r CI&PIOCrHdCiHlr44-*h. .
CHIPCL GHIPC~S CIHIPC~ CtKIPCTr CI&PcL
cI&PcL
Propylene oxide Propylene oxide Ct&OH eClCtHtOH o-cresol p(fef-CIHii) &&OH
100 100 40
le
Rdemnwr
'C. lOl-l02/15 mm. 235 l34.6/7 mm.
CHiP(OC;&)i. CHiP(0CiHdr. CH:P(OCiHi-iso)r. Cd&P(OCHi)r.. CiHJP(OC1HI)r.. .
. .. . . . . . . . . . ....... , , . . , . . . . .. . . . . . . . . . . . .... ... .. . .. . .. . . . . . . . . . .
Roiling Poink
aaa-229/11 mm. 128.b a a 6 1 1 mm. 8aQ-a3l/lO mm. ZabaaB/a mm.
(9) (8, 1713 ( 10)
(251) (236) (236) (67, 101)
411
T H E PHOSPHONOUS ACIDB AND THEIR DERIVATIVE8
TABLE 13 Phoaphonowr dieelers prepared bi/ lransealerificath
I Phosphonous Diester
-
CHIP(OCH:CHISCIHI)I.,........................... CHiP(0CaHir-n): ................................... CHaP(OCioHii-n)i.. ................................ C:HiP(OCiHim)r. ................................. CiHiP(OCioHri-n)i. ................................. CIHIP(OCIHI)I.................................... CHIP(OCHI)OCHICHISC~HI ........................ CHaP(0CxHi)OCHiCHiSCiHi. ....................... CHiP(OCiHr)OCH:C&SCiHi.. ................
.
CHiP(0CiHrwo)OCH:CHiSCiHi.....................
..... ........
CHiP(0CrHi)OCoHn-n.. CHiP(0C:Hi)OCioHii-n . ............................ CrHaP(0CrHi)OCaHim. C:%P(OCiHi)OCioHii-n. ........ C:HIP(OCIH~)OC~HI. ..............................
4. Reaction with halogens Phosphonous diesters react quantitatively with bromine (297), giving products of unspecified structure. By analogy with the phosphites, however, these products are probably phosphonobromidic esters:
+ Brr
-+
R’P(O)(OR)Br f RBr
6. The Arbuzoo reaction
Phosphonous diesters undergo the Arbuzov rearrangement with a wide variety of organic halides, giving esters of secondary phosphinic acids: RP(0R)z
+ R‘X
+
RR’P(0)OR
+ RX
The organic halides may be simple alkyl halides (8, 11, 14, 16, 19,21, 57, 101, 107, 110, 149, 150, 161,219, 260,291, 294,295,297,305, 316,324), triphenylmethyl bromide (ll), carbon tetrahalides (19, 143, 144, 145, 147, 16l), a-halo esters (10, 19, 38), chloromethyl methyl ether (16), 2-chloroethyl ethyl ether (16), chloromethyl ethyl sulfide (181),2-bromoethyl acetate (110),glycol bis(ch1oroformates) or their thio analogs (106), a-halo malonates (13), /?-bromo nitriles (38), carbamoyl chlorides (19), octachlorocyclohexa-1,4diene (286), his(/?-bromoalkyl) phosphonates (47), Cchloro-PIP-diphenoxyisophosphazoacyls (68), or certain a-halo ketones (277).Alkyltin halides were a t first believed to give products containing phosphorus-tin bonds (17), but are now known to give products with P - 0 4 n bonds (18),probably owing to self-isomerization before reaction with the alkyltin halide. The reaction with alkyl halides is usually complete in 2-3 hr. a t 100-12OoC., compared to the 5-6 hr. a t 160°C. required for trialkyl phosphites. The use of the higher temperature is sometimes deleterious, as the product may break down to a free phosphinic acid and
Alcohol per cent
CHiP(0R): (R CHI, CaHr, or iso-CaHr) CHiP(0CrHih CHiP(0CiHdr CiHiP(0C:Hi)i CrHiP(0CrHi)r CtHsP(0CiHi): CHaP(OCH3i CHiP(0CiHih CHiP(0CiHr)r CHiP(0CiHriso)i CHIP(0C i H h CHiP(0CrHdi C:HaP(OC:Hr)r CrHiP(0C:Hd: CrHiP(0CrHi)n
bon disulfide, and from the tertiary phosphites, which give no color with carbon disulfide (305).
R’P(OR),
1
Preparation from Phoaphonous dieater
CYH~SCHICH~OH n-CIHlrOH n-ClaHuOH n-CiHuOH n-CmHnOH CIHgOH (Na) C1HsSCHrCHiOH CrH&EH:CHrOH CIHISCHZCHIOH CYHBSCH: CHiOH n-CsHuOH n-CroHnlOH n-CIHIrOII n-CloHtlOH CaHiOH
0
References
C.
W84/0.026 mm.
30
135-130/0.3 mm. 138/0.076 mm. 123/0.05 mm. 150/0.05 mm. 126128/16 mm. 42-43/0.04mm. 40/0.04 mm. 53-66/0.026 mm. 42-46/0.1 mm. 66/0.1 mm. 85/0.26 mm. 72/0.3mm. lOO/O.O6 mm. 6 1 / 0 . 0 8 mm.
78 a4 a4 24 45
an alkene (11, 14, 295). In these cases the rearrangement may be carried out at a lower temperature, using a dialkylaniline as a catalyst (14,181). The increased ease of reaction of phosphonous diesters is also manifested in the partial isomerization of some esters during their preparation. Dimethyl phenylphosphonite, for example, undergoes extensive isomerization on heating, and a mixture of products is obtained whether the ester is prepared by the alkoxide method (9) or by the alcohol/tertiary amine method (14, 16, 150). Alkylene dihalides [X(CH&,X, where n = 3 to rj] react with phosphonous diesters giving secondary phosphinic acid phostones (compare phosphonous acid phostones, Section VIII,A,4). Both ester groups are split out (90) : C&.P(OC&.)Z4- Br( CH&Br
4
CtHI$(0)CH~CH&Hd!l
+ %C,HaBr
Phenolic esters of phosphonous acids, as might be expected, do not undergo the Arbuzov rearrangement except on drastic heating (15, 145, 146). The alkyl halide adducts can, however, be decomposed with alcohols (the Landauer-Rydon reaction), giving secondary phosphinic esters (15): CsHsP(OCsH&.CHaI
+ CzHsOH
4
ce&F’(O)Oca”s
+ CsBsOH + CJ%I
AH,
or with sodium hydroxide (238):
+
CH&sH4P(OCsH~)z.CsH~CHlCl NaOH -+ CH&sH4P(0)OC~HIf NaCl
+ C&OH
bH&s&
Phosphonous diesters react with a,P-unsaturated acids, giving saturated esters. The reaction probably proceeds through an Arbuzov-type mechanism, in which the anionic end of the molecule in the quasi-
412
ARLEN W. FRANK
phosphonium intermediate assumes the function of the halide ion (151). CgHaP(0R)z
+ CHFCHCOOH
4
CgHsP(O)(0R)CHzCHnCOOR
A similar reaction occurs with a,B-unsaturated aldehydes, such as acrolein (151). The products are distillable with difficulty, and only the ethyl ester given below has been isolated in pure form.
+ CHz=CHCHO
between the dialkyl phosphonites and the much better known trialkyl phosphites. V. PHORPHONODITHIOUS ESTERS The phosphonodithious esters, R'P(SR)I, are liquids with unpleasant' odors, but unlike their oxygen counterparts are not appreciably oxidized in air (26). A. SYNTHESIS
The methods used for preparing phosphonous diesters from phosphonous dihalides may also be applied CSHP,P( 0)(OC2Hs)CHzCH=CHOCzH* to their sulfur analogs. The phosphonous dihalide can Phosphonous diesters react with sultones in the folbe added to an ether solution containing sodium and a lowing manner (105) : mercaptan (12) or to an ether solution containing a r--1 mercaptan and a tertiary amine (26). The former CsHsP(OC4Ho)t OCHnCHzCH2SOa 4 met'hod was used to prepare diethyl phenylphosphonoCsHsP(O)(OCIHo)CH1CHzCHaS(~rCIHo dithioite, b.p. 143-144"C./3.5 mm., and diisobutyl 6. Anomalous A rbuzov reactions phenylphosphonodithioite, b.p. 191-192"C./12.5 mm., from phenylphosphonous dichloride and the appropriate Phosphonous diesters undergo several so-called mercaptide (12); the latter method was used to prepare "anomalous" Arbuzov reactions, which are anomalous diethyl ethylphosphonodithioite, b.p. 98-1OOoC./10 in that no new carbon-phosphorus bond is formed. mm., from ethylphosphonous dichloride, ethyl merVinyl esters of phosphonic acids are formed in the reaccaptan, and pyridine in 74 per cent yield (26). tion of phosphonous diesters with a-halo aldehydes The synthesis of phosphonous diesters from trialkyl (4, 185, 300, 312, 345, 346): phosphite8 and Grignard reagents has also been apRP(0R')r + CC1,CHO RP(O)(OR')OCH=CClz + R'CI plied to the dithious esters. Dipropyl butylphosphonodithioite, b.p. 110-112"C./2.5 mm., was prepared from a-Halo ketones may give either the anomalous prod(C,HB>,P and butylmagnesium chloride in 25 per cent uct as i~ the equation above, or the normal product of yield (305). an Arbuzov rearrangement, or a mixture of both, depeiiding on the halogen employed and the temperahre B. REACTIONS of trhe reaction (277, 345, 346). The formation of the The phosphonodithioites undergo many of the reacnormal product is more favorable, however, for phostions characteristic of the phosphonous diesters. They phonous diesters than for phosphites, because of the combine readily with sulfur in the absence of a catgreater ease with which the phosphonites undergo the alyst, and form sirupy complexes with copper monoArbuzov rearrangement. halides (12, 26). The Arbuzov rearrangement with Diethyl phenylphosphonite reacts with 2-bromo-2alkyl halides (12), a- or &halo esters (12), or glycol nitropropane giving an isopropylideneamino phosphochloroformates (106) proceeds normally, giving esters nate (3): of phosphinothionjc acids. In some cases the second 2CsHsP(OCIHs)r (CH&C(NOz)Br thioester group is also eliminated as alkylsulfenyl CsHsP(O)(OCIH~)ON=C(CHA CsHsP(O)(OCtHa)r CaHsBr halide (26). The phosphonodithious esters differ in this This may be considered to be an anomalous Arbuzov respect from the trithiophosphites, (RS)J?, which give reaction complicated by an additional redox reaction only the products of addition to sulfur, not to phosbetween the nitro group and the phosphonite. phorus, under the conditions of the Arbuzov readion. CgHsP(0CzHs)l
-+
+
-+
+
+
-+
+
7. Related reactions
Reactions which are closely related to the Arbuzov reaction in that they appear to proceed by a common mechanism occur when phosphonous diesters are treated with isothiocyanates (255), disulfides (256), or sulfenyl chlorides (261) :
+ C6HsP(OCtHs)r + RSSR CaHsP(OCIHs)* + RSCl
CIHKP(OC~H~)~ RNCS
-+
-+ -+
+ C2HsCN CaHsP(O)(OCzHs)SR + CaHsSR CaHsP(O)(OCzHs)SR + CzHsCl CgHsP(O)(OCzHs)SR
In all of these reactions a close analogy may be drawn
VI. PHOSPHONOUS DIAMIDES AND IMINOPHOSPHINES Phosphonous dihalides react readily with primary and secondary amines giving compounds containing phosphorus-nitrogen bonds. The literature contains few references to substances of this type despite their ease of preparation and their demonstrated usefulness as intermediates in the Arbuzov reaction (Michaelis, 18921903). A. SYNTHESIS
The reaction of phosphonous dichlorides with pri-
4 13
T H E PH08PHONOIJR ACIDS AND THEIR DERIVATIVES
mary or secondary amines is violent if the reagents are simply mixed together. In practice a solvent such aR ether is used, and the amine is added in sufficient excess to bind the hydrogen chloride that is evolved. With phenylhydrazine the reaction is vigorous at the start hut requires long standing at room temperature for completion (234) : RPCli
+ 3CeHrNHNH2
4
RP=NNHCsHs
+ 2CoHsNHNHs.HCI
The products are iminophosphines. In one case a small amount of the dihydrazide, CaHsP(NHNHC&f&, was also isolated (249). Secondary amines such as piperidine or tetrahydroquinoline give phosphonous diamides: RPClr
+ 4CsHloNH
+
RP(NC6Hio)a
+ 2CsHlaNH.HCI
Phosphonous dichlorides do not form cyclic phosphorus-nitrogen compounds with amine hydrochloides (239). A list of the known phosphonous diamides and iminophosphines is given in table 14. R . REACTIONS
Little is known of the chemistry of iminophosphines and phosphonous diamides. The iminophosphines are converted to salts of the corresponding phosphonous acids by boiling water (234, 235, 236, 249).
+
RP=NNHCOHK 2Ht0
5
RPH(O)OH.NH~NHC~HI
Phosphonous diamides are stable to boiling water but are hydrolyzed by dilute acids (237). Treatment with anhydrous hydrogen chloride in benzene solution pre-
cipitates the amine hydrochloride (237). In other reactions the phosphonous diamides behave as typical compounds of trivalent phosphor,us. They add sulfur at 130°C. giving phosphonothioic diamides, form adducts witth carbon disulfide, and react with chlorine giving dichlorides which may be hydrolyzed to phosphonic diamides (237). They form quaternary salts with alkyl halides (237) in which the alkyl group is attached to phosphorus, not nitrogen. A reaction peculiar to the phosphonous diamides constitutes a variant) of the well-known Arbuzov reaction. The quaternary salts formed by the action of alkyl halides on the phosphonous diamides may be transformed into the quaternary hydroxides by treatment with silver oxide. These, on heating, split out the amine, giving secondary phosphinic acids (237) : [RP(NCsHta)*CHa]+OH-
+ HIO
+
R(CH,)P(O)OH
+ 2C~Hio"
VII. PHOSPHONOUS EEITER CHLORIDES, AMIDECHLORIDES, AND ESTER AMIDES The presence of two replaceable hydroxyl functions in the phosphonoua acids (as written in the form containing trivalent phosphorus) makes possible the existence of mixed ester chlorides, amide chlorides, and ester amides which have no counterparts in the carboxylic acids. The chemistry of this singularly interesting group of substances has not, however, been adequately studied. A. PHOSPHONOCHLORIDOUS ESTERS
The reaction of a phosphonous dichloride with an alcohol and a tertiary amine in equimolar proportions
TABLE 14 Phosphonous diamides and iminophosphines
I Product
I
Preparation from Phosphonous dichloride
Melting
1
Boiling
I
Amine
Iininoptrosphines (from primary amines)
c.
oc. C~HIP--=N N LICEHI.. . . . . . . . . . . C I I I ~ P = N N H C O H ~ C H I. -.~... . . CI€iIP3NN(OHI)CHrC~H,.. . . ~ - C I C I I I ~ P = N N H C ~ H. I. .. . . . . ~ - B ~ C ~ H I P = N N I I C I H., . . . . . . . . . . 4-BrCsK4PCL ~-C~HIC~HIP=NN€IC . .~. H . .~. . . . . . 4-CrHsCsHhPCh ~ , ~ , ~ - ( C ~ I ~ ) : C ~ H ~ P = N .N. H . . C. .I. H ' 2,4,0-(CHi)rCsHzPCh
I'hanyl hydrazine
.
pTolylhyrlranine CsIIrCIIr(C:sHd NNHr Phenyl hy(lrazine I'honylIqrlrar,ine Phenylhydrazine I'lrenylhydrszine
CIHIP(NC1Hin)l. . . . . . . . . . . . . . . . . .
CIIiPBri CsHiPClr
Diitdhylarnine PipnriGline
CaHIP(NCnIlin)r. . . . . . . . . . . . . . . . . . . ~ - C I C I H ~ P ( N C I H.I.O. ).~. . . . . . . . . . . 4-ClirC~€1~P(MC1Hin)r ............... ~ - C H ~ C I H ~ P ( N C V. H . .~. O . .).~. . . . . . . CCHIOCIH~P(NCIHI~)S ............. ~-CSHIOCIH~P(NCIHI~)S
C~HIPCIY 4-CICsH4PClr ~-CHIC~H~PCI~ 4-CHaCdW"lr 4-CHaOCsH4PClr ~C~HIOGH~PCI:
Tetrslivdroqiiinoline Pilwridine Piperidine Tetr~hydro~tilnoline Piperidine Piperidlne
---
159 102 141 161 ((1.) 160 139 138
78
(249) (240) (249) (231)
I
1
150
95 a5
140 09
84
(234) (235)
~
I
(236)
137-141
(190) (71, 237. 340) (237) (1137) (237, 340) (237) (237) (237)
_- -.
414
ARLEN W. FRANK
a t 10-20°C. leads to the replacement of one of the chlorine atoms, forming a phosphonochloridous ester (118). RPCIz
+ R’OH + (C&)aN
+
RP(0R’)CI
+ (CaHs)rN*HCl
Treatment of this product directly in solution with sulfur flowers gives a phosphonochloridothionate in 25-28 per cent overall yield (118). The intermediate phosphonochloridous esters have not been isolated.
+S
RP(0R‘)Cl
.--)
RP(S)(OR’)Cl
Interestingly, the addition of sulfur to the phosphonochloridite proceeds readily at 25-35OC. in the absence of a catalyst (118). Phosphonous dichlorides require a catalyst (aluminum chloride), but phosphonous diesters do not (see Sections III,B,5 and IV,B,2). E. PHOSPHONAMIDOUS CHLORIDES
Phosphonamidous chlorides may be synthesized by the reaction of a phosphonous dichloride with two equivalents of a secondary amine (25) : CaHsPCL
+ 2(CzHs)rNH
+
+
CzHaPIN(GHO~IC1 (CiHI)zNH *HCl
These amide chlorides react with water with bursts of flame and are rapidly decomposed in air with the separation of the amine hydrochloride (25). Treatment with an alcohol gives diethylamine hydrochloride and a phosphonous diester (25). C,HsP[N(CgHs)n]CI
+ 2CzHoOH
4
CiHsP(OCnH&
the presence of aluminum chloride, giving phosphonamidothioic chlorides (25). No reaction occurs in the absence of the catalyst.
+ (CzHs)nNH*HCl
In the presence of a tertiary amine only the halogen atom is replaced (see Section VI1,C). Phosphonamidous chlorides combine with sulfur in
+ 2 C~HBP(S)[N(CIH&]C~
CIH~P[N(C~HK),]CIS
The known phosphonamidous chlorides are listed in table 15. C. PHOSPHONAMIDOUS E8TERS
Phosphonnmidous esters are prepared by the action of alcohols on phosphonamidous chlorides in the presence of 8 tertiary amine (25). The yields for the lower alkyl members range from 60 to 70 per cent. The ester amides are colorless mobile liquids with unpleasant odors. CzHsP [N(GHs)z]C1
Chloride
Cr&P[N(CHdrlCI .............................. .............................. C~HIP[N(C~&)~]CI
C~ILP[N(CH:)~]OCIHI-~~O.
..
....
CZHIP[N(C:H~I]OCHI.. ................ CrHrP[N(CrHr)r]OCtHr. . . . . . . . . . . . . . . . . . . . . . . . . . CaHrP [N(CrIt)t]OCrH7. ......................... CrHrP [N(CrHr)r]OCaH7-iso. ...................... CrHrP[N(CrHdrIOCdHr. ......................... CrHrPIN(C:Hr)r]OCdHr~. ...................... CrHrP [N(Cr&)r]OCrHim. . . . . . . . . . . . . . . . . . . . CrHrP[N(CrIt)il0C1Hirn. ....................... C r E P [N(CrHr)tlOCaH~r-n
......................
C~&PIN(CIHI)~~OCI~HI~-~.
CrHrPCIr CaHrPCL
CdHoOH
+
C&P [N(CtHs)a]OCdH,
In the absence of the tertiary amine the amide group is cleaved and the product is a phosphonous diester (see preceding section). The phosphonamidous esters combine readily with 6ulfur, giving esters of phosphonamidothionic acids (25), and take part in the so-called “anomalous” Arbuzov reaction in a manner similar to the phosphonous diesters (300, 312, 346). The reaction with chloral (300) procesds as follows:
+
CaHsP(N&)OC:H&o
CClSCHO 4 C*HcP(O)(N&)OCH=CClr
+ iso-CIH7C1
The known phosphonamidous esters are listed in table 15. VIII. PHOSPHONOUS MONOESTERS The partial esters of phosphonous acids are relative newcomers to the family of organophosphorus compounds, owing perhaps to indications in the early litera-
Preparation from Produot
+
I Amino
I
1 1 Yield
or alaohol
I p”,:.,’1 ~
(CHhNH (CrHdrNH
iso-CrHtOH CHrOH CaHrOH CiHiOH iso-CaHTOH CdHoOH iso-CdHmOH n-CsHirOH n-GHirOH n-C,HiiOH n-CiHi:OH ~-CIOH:IOH
Boiling Point
~
63 66
61 62 71 61 40 30
zr
22
~
~
~~~~
C.
61-52/16 mm. 62-53/3 mm.
71-73/27 mm. 49-50/10 mm. 63-54/9 mm. 73-74/10 mm. 63-85/10 mm. 86-89/10 mm. 78-80/10 mm. 80-81/1 mm. lOl-l02/1 mm. 116-116/2 mm. 121-122/2 mm. 134-l36/2 mm.
Referenoe
415
THE PHOSPHONOUS ACIDS AND THEIR DERIVATIVES
ture that they were unstable. In 1877 Kohler and Michaelis (171) observed that diethyl phenylphosphonite, though not soluble in water, was gradually decomposed by it to a partial ester which was identified by analysis as ethyl hydrogen phenylphosphonite. On further contact with water this ester formed an unstable crystalline hydrate and in time was converted to the acid, phenylphosphonous acid. CdIsP(0CgHo)r
--+
CsHsPH(0)OCsHr
--+
C&PH(O)OH
Kosolapoff (174) prepared this same ester by the method described in Section VIII,A,2 and noted that it developed an extremely foul phosphine-like odor on distillation. However, there is some question as to whether the ethyl ester differs in this respect from other members of the series (71, 281, 305). The partial esters of alkylphosphonous acids are for the most part colorless, mobile, evil-smelling liquids (20). The higher alkyl esters (C, to do not wet glass (20). A. SYNTHESIS OF PHOSPHONOUS MONOESTERS
1 . F r m phosphorochloridites with Grignard reagents
The synthesis of phosphonous diesters by the reaction of Grignard reagents with dialkyl phosphorochloridites was described in a previous section (Section IV,A, 1). Direct hydrolysis of the reaction mixture with 5 per cent aqueous ammonium chloride yields the monoesters instead of the diesters (139). The products are described in table 16.
+ R’MgX R’P(OR), + MgXCl NH4Cl R’P(0R)r + HIO + R’PH(0)OR + ROH
(R0):PCl
--+
R‘P(0R)r
R’PClr
+ 2ROH
+
R’P(0R)t
R‘PH(0)OR
--+
+ RCl
If the temperature is allowed to rise, the second ester group may also be split out; it will be remembered that alcoholysis of phosphonous dichlorides is a good method of preparing phosphonous acids (see Section II,A,4). A better technique for preparing monoesters is to add the alcohol in a. slow stream under the surface of the phosphonous dichloride while keeping the system under slightly reduced pressure to draw off the hydrogen chloride as it is formed (20, 281). Acid-sensitive monoesters may be prepared by the reaction of phosphonous dichlorides with alcohols in the presence of one equivalent of a tertiary amine such as pyridine (107, 269). The phosphonous monoesters prepared by this method are given in table 17. 3. From phosphonous diesters
The partial hydrolysis of phosphonous diesters takes place slowly in neutral (171) or basic medium, but with a trace of acid the partial esters are instantly produced in almost quantitative yield (305) : R’P(0R)a f Ha0
H+ --+
R’PH(0)OR f ROH
The removal of one of the benzyl groups in dibenzyl esters can be accomplished with lithium chloride in 2ethoxyethanol (5). Phosphonous acid esters prepared by these methods are listed in table 18. The preparation of partial esters by the reaction of a phosphonous diester with the corresponding phosphonous acid is described in Section VIII,A,4.
W. From phosphonous dichlorides Partial esters of phosphonous acids are formed when a phosphonous dichloride is added to an alcohol at ice-cold temperatures (20, 174, 275, 281). In the absence of a tertiary amine, the phosphonous diester initially formed is attacked by the hydrogen chloride, generating the monoester and liberating alkyl chloride :
+ HCI
4.. From phosphonous
acids
A variety of methods have been described for preparing partial esters of phosphonous acids from the acids themselves. A classical method is the reaction of a silver salt of a phosphonous acid with an alkyl halide (111, 209, 217):
+ 2HCl
RPH(0)OAg
+ RI
+
RPH(0)OR
+ AgI
TABLE 16 Phosphonous monoesters prepared from phosphorochloridites Preparation from Phosphonous Monoester Phosphorochloridite CHaPH(O)OC4Ht. .............................. CiHiPH(O)OC4He .............................. CIHTPH(O)OC~H~. ............................. I.~-CBHIPH(O)OC~HI ........................... C4HePH(O)OCiHi. ............................. I ~ F C ~ H ~ P H ( O ) O C I.......................... HI. CIH~CHIPH(O)OC~TI. ......................... CJLPH(O)OC~HI..............................
(C4HaO)iPCI (C4HaO)rPCI (C4HoO)rPCI (C4HsOhPCI (CrH,O)rPCI (C~FLOhPC1 (C4HaO)rPCI (C4HiO)iPCl
I
Yield
Boiling Point
orignard reagent CHiMgX CiHiMgX CiHiMgX iso-CiHIMgX C4HsMgX iso-C4HiMgX CaHaCHiMgX CiHiMgX
p e t cent 66 63 00 69 66
64 68 68
C.
47-48/2 mm. 84-06/10 mm. 07-07.6/2 mm. 68.6-60.2/2.6 mm. 40-49.6/1.6 mm. 70-77/0 mm. 113-116. S / Z mm. 98.2-100/1 mm.
Reference
416
ARLEN W. FRANK
TABLE
17
Phosphonow monoesters prepared from phosphmunrs dichlorides
I
Preparstlon from ~~
Phosphonous Monoaster
Yield
Phosphonour diohloride
Boiling Point
"C.
psr wnl
C:H,PH(O)OCH1. .................... CIHIPH(O)OC&I.. . . . . . . . . . . . . . . . . . . CrHiPH(0)OCiHt. . . . . . ...... CrHiPH(0)OCaHriso. ................ CSHIPH(O)OC~HI. ................... CSHIPH(O)OC~HI-IEO CrHIPH(0)OCaHia-n. . . . . . . . . . . . . . . . . . Cr&PH(O)OC~Hirn CrHiPH(0)OCIHirn Cc&PH(O)OCsHis-n CrHiPH(0)OCioHri-n .
CrHrPClr CIHIPCII CrHiPClr CiHiPCIi CIILPCll CaHiPCh CsHiPClr C~HIPCIY CIHIPCIS CIHSPCI: CI HiP CI I CIH~PCII CIHIPCI: CsHiPCls CiHiPCl: CiHiPClr CiHiPCh CnHiPClr CsHiPClr CiHiPCli CnHiPCIr CnHiPCIa CnHrPCIr CIH~PCI:
................
C:HIPH(O)OCHSC~HI. . . . . . . . . . . . . . . CiHiPH(O)OCH1. .................... CaHrPH (0)OCrHi CaHiPH(0)OCdHs C~HIPH(O) OCaHi C~HIPH(O)OCIHI CnHiPH(0)OCnHirn. . . . . . . . . . . . . . . . . . CiHiPH(0)OCsHim. . . . . . . . . . . . . . . CeHIPH(0)OCHsCnHi . . . . . . . . . . . . . . . . Ci&PH(O)O(CHr)~SI(CHI)I.. . . . . . . . .
.I
CHlOH CtHiOH CiHiOH Iw-CIHIOH CdHsOH iso-C4H&H n-CnHiaOH n-CvHiiOH n-CIHITOH n-CIHwOH n-CtoHriOH CsHrCHrOH CHIOH Cr&OH iso-CIHiOH CHsCHCHrOH CdHsOH ~~o-CIHSOH n-CnHiiOH n-CiHlsOH n-CIHiiOH n-CIHieOH CaHiCHrOH (CH~IRI(CH~~OH
Acid- or base-catalyzed esterifications with alcohols have been described in a few instances. Allyl hydrogen octylphosphonite was prepared by esterification of octylphosphonous acid with allyl alcohol in the presence of a catalytic amount of ptoluenesulfonic acid, with azeotropic removal of the water (107). Esters of triphenylmethylphosphonous acid have been prepared by alkylation with dialkyl sulfates and potassium carbonate (111). Glycol esters of phosphonous acids were prepared by treatment with ethylene oxide in the presence of catalysts such as sodium hydroxide or silica gel (320, 321). Aliphatic phosphonous acids which contain a hydroxyl group in the 3- or 4-position form cyclic esters on mild heating (316). The products are called "phostones," by analogy with the lactones of the carboxylic acid series. Partial eaters of phosphonous acids may also be prepared by heating the acids with the corresponding phosphonous diesters (334) : C&PH(O)OH
+ CcHS(OR), 3
Rderenew
Aloohol
2CsHiF"(O)OR
20
6&66/ll mm.
ai
68-69/9 mm.
47 42
81-82/10 mm. 69-70/10 mm.
67 66
92-93/9 mm.
86-87/9 mm. 87-88/1 . 6 mm.
14 42
9!&100/4 mm.
62 69
88
102-103/1 mm. 122-123/4 mm. 129-130/1.5mm. 90-95/0.1min. 91-93/1 mm. 94-95/1 nun. lO6-lW/l mm. 121-123/1,6mm. 90.E-92/0.12 mm. 112-113/1 mm.
60
139/1 mm.
80 78 67 93
l50/l mm. 155/1 mm. 158-160/1 mm. 90-95/0.06 mm. 142-148/1 mm.
49 85
66 84 70 80
(20) (20) (20) (20) (20) (20)
(zo) (20) (20) (20) (20)
(5) (275,281) (71,174,276,281) (276,281) (107)
(127,174) (276,281) (276,281) (275.281) (275,381) (275, 281)
(6)
(iW
This reaction takes place at 1W160°C. and the yield is quantitative. Partial esters prepared by these methods are listed in table 19, together with the method of preparation.
B. REACTIONS OF PHOSPHONOUS MONOESTERS
The hydrolysis of phosphonous monoesters to pho8phonous acids is described in Sections IIJAJ5and II,A,4 and discussed in the introduction to Section VIII. Reactions of phosphonous monoesters with phosphonous dichlorides or phosphinous chlorides to form mixed anhydrides are described in Section X. Phosphonous monoesters react with oxygen, sulfur, halogens, etc., giving phosphonic acids or their derivatives. These reactions are formally regarded in the following discussion as addition reactions to the esters in the tautomeric form containing trivalent phosphorus [i.e., as RP(OR')OH], but alternative mechanisms involving direct displacement of the hydrogen attached to phosphorus should not be considered ruled out.
TABLE 18 Phosphaous monoesters prepared from phoaphonous diesters Phosphonous Monoester CIHsPH(0)OCrHi. ........................... CeHrCHrPH(0)OCrHi ........................ GHIPH(O)OCIHI............................ CaELPH(0)OCHaCJIi. .......................
Phosphonous Dierter C4HnP(OCrHh CIH~CH:P(OCI&): CaHiP(0CaHi)r CnHIP(0CHsCaHi)r (LiCI)
Yield
Boiling Point
psr ernt 85
OC.
68
106/15 mm. ll9/3 mm. 119-121/4 mm.
Referenoe
(am) (305)
(aoa)
(5)
417
? H E PHOSPHONOUS ACIDS AND THEIR DERIVATIVES
TABLE 10 Phosphonoiur monoesters prepared from phosphonous acids
-
Reactants Used
Phosphonous Monoester
Melting Point
Yield
Boiling Point
__ ___-
-r
CHaCH(CHt)CHaPH(O)O . . . . . . . . . . . . . . . . . . . . . . . . n-CmHnCH=CHPIi(O) (0CHrCHa)tOH.. . . . . . . . . . .
n-CnHasCH=C€IPH(O)(OCHaCHa)sOH.. .......... COHIPH(O)OCHSCIISCI. ......... Ca1-11PHfO)OCaH1r-iso.. . . . . . . . . . . . . . . . . . . . . . . . . CoHaPH(0)OCsHI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(CHn)aCOHPH(O)OAg. CHiI (CHt)rCOHPH(O)OAg, CalId C~HICHOHPH(O)OA~, CHI1 (CaHdaCPH(O)OAu, CrHiI ~ - C I H I I P O ~CHa=CHCHiOII H~, (C~HI)~CPOIH:, (CHa)tSO4 (CaIIdaCPOaH,, (CaHdaSOr
2. Reaction with halogens
Phosphonous monoesters react with halogens, giving alkyl phosphonochloridates (5, 127, 292, 334) : 4
CzHsP(O)(OR)Cl
+ HCl
3. Reaction with amines and carbon tetrachloride Phosphonous monoesters react with amines and carbon tetrachloride in the following manner (5) :
+
+
C~HKPH(O)OCH~C~HK CCld 2CsHiiNH2 4 CsHsP(O)(OCHaCaHs)NHCsH11 CsHllNH?.HCl
+
+ CHCk
The product, is a phosphonamidate.
4. Condensation reactions Condensation reactions of phosphonous monoesters have been studied rather extensively in recent years, since reliable methods for their synthesis have been developed. Phosphonous monoesters undergo base-catalyzed condensation reactions with a wide variety of a,P-unsaturated compounds. As an example may be given the reaction with qP-unsaturated esters (38, 275, 281, 282) :
+
134/1 mm. 163-164 118-121.6 100-104/0.2 m m .
___
The base-catalyzed addition of sulfur to phosphonous monoesters gives monoesters of phosphonothionic acids (39) :
+ CI
99 118-121.5
H O C I I ~ C H ( C H I ) C H ~ P O(heat) ~H~ CnHiaPOtHt, ethylene oxide 100 CMH~POYH ethylene ~, oxide 100 CsHIPOaHi, CaHiP(OCHrCHiC1): CaHaPO:Ha, COHIP(OCIHI~-~EO): CeHiPOrHa, COHIP(OCIHS)S
1 . Addition of sulfur
CzHsPH(0)OR
c.
e C.
er cent
(CHa)aCORPH(O)OCHa.. . . . . . . . . . . . . . . . . . . . . . . ( C H ~ ) ~ C O H P H ( O ) O G H. I. . . . . . . . . . . . . . . . . . . . CIHICHOHPH(0)OCHa. . . . . . . . . . . . . . . . . . . . . ( G H I )tCPH (0) OGHi . . . . . . . . . . . . . . . . . . . . . . . . . ~-CIHI~PH(O)OCH~CII=CH~ ..... (CaHi)aCPH(O)OCHa, . . . . . . . ..... (CaHi)rCPH(O)OCiHb.. . . . . . . . . . . . . . . . . . . . . . . . . . .
CzHrONa
C~HKPH(O)OR CH?=CHCOOCHj CeHsP(0)(OR)CHzCH&OOCHa
With esters of aliphatic phosphonous acids it is necessary to use the same alkyl radical in the alkoxide as in the ester (281). This is not the case with esters of aromatic phosphonous acids (281). Phosphonous acid esters also react with a,@-unsaturated ketones (280), a,B-unsaturated nitriles (38, 279), a,&unsaturated phosphonic esters (279, 283),
vinyl acetate (278), and 2-vinylpyridine (218). The mechanism of these reactions is presumed to be a nucleophilic attack on the polarized olefinic double bond, resembling the Michael addition (38). Proof that the addition takes place in this manner (in the opposite sense t o Markownikov’s rule) has been given in one irist,ance (38). The reaction of alkyl halides with the sodium derivatives of phosphonous acid esters provides a useful method for the synthesis of secondary phosphinic esters (24, 139, 174). A molar amount of sodium is necessary. CaHsPH(0)OR
2
C6HsP(0)(0 R ) N a
R’X
*
CsH5R’P(0)OR
When diethylcarbamoyl chloride is used in this reaction, the product is an ester of diethylamidoformylphosphonic acid (23). a-Hydroxy- and a-aminoalkylphosphinic acids may be prepared by the reaction of ketones (2, 136) or Schiff bases (136, 276) with phosphonous monoesters, in a manner similar to the reactions with hypophosphororis acid (Section II,A,3). A basic catalyst is used.
+ CaHsPH(O)OCIHs + CsHsCH=NHCsHs
C~HKPH(O)OC~H,CHaCOCHa 4 (CHa)zC(OH)P(O) (OC2H,)CsHs 4
C~HKCHNHCEHK
I
P(0)(OCZHK)C~H~
The Schiff base may be formed in situ, as in the reaction of ethyl hydrogen phenylphosphonite with acetone and ammonia (136). The yields are poor in this case, owing to side reactions. A reaction with ethyl isocyanate has also been described, addition taking place across the C=N bond (278). Phosphonous monoesters add also to the C--C bond in thiourea (1). C~HKPH(O)OR -I- SC(”a)r
+
(NHz)zCP(O)(OR)CsH6
I
SH
Phosphonous monoesters add to olefins in the presence of free-radical initiators such as di-tert-butyl per-
418
ARLEN W . FRANK
oxide, giving esters of secondary phosphiiiic acids (325). For example, ethyl hydrogen phenylphosphonite reacts with 1-octene, giving ethyl octylphenylphosphinate in 19 per cent yield: CaHZH(O)OCtHs
+ CsBlsCH4Hr
4
QHnP(0)OCzHr A6H6
The polymerization of allyl hydrogen octylphosphonite with di-tert-butyl peroxide takes place at 120OC. to give a product which is probably a mixture of PH/olefin polymer and allyl homopolymer (107). The extent of each is not known. Copolymers with diallyl phthalate have also been described (107).
IX. PHOSPHONOTHIOUS ESTERS Only one compound of this type is known. The reaction of butyl ethylphosphonochloridite with hydrogen sulfide gives butyl ethylphosphonothioite, b.p. 107108OC./15 nim., in 50 per cent yield (254).
+
~ H s P ( o c ~ H o ) C l HzS
+
CzHZH(S)OCdHo
+ HCI
X. PHOSPHONOUS ANHYDRIDES Three classes of phosphonous anhydrides are known: (1) mixed aihydrides of phosphonous and phosphorous acids, (8) true anhydrides of phosphonous acids, and (3) mixed anhydrides of phosphonous and phosphinous acids, The anhydrides of low molecular weight are distillable liquids of unpleasrtnt odor which react with moisture and oxygen of the air, and which cause cotton to smolder.
CzH,PCI* CdW"1r
+ 2(RO),P(O)Na
+
GH#(OP(ORh]~
-+
+ 2(RO)rP(O)H + (GHrhN
-+
C*HsP[OP(ORb]r
2NoCI
+ 2(GHr),N*HCI
Reactione of this type are listed in table 20. The first member of the series, the dimethyl ester, was apparently produced in the reaction but exploded on attempted ditsillation. 8. From phosphonous dichlorides wilh phosphonous monoesters
A reaction analogous to the above, using a phosphonous monoester, isopropyl hydrogen ethylphosphonite, instead of a dialkyl phosphite, gave in the presence of triethylamine an unstated yield of anhydride, b.p. 144-146OC./l mm. (26). C,HrPClr
+ C*HsPH(0)OCSHrieo
(CrHd8N 4
GHP(OP(C~H~)(OCSH~~~O)I~ 9. From phosphonous monoesters with
phosphinous chlorides Mixed anhydrides of phosphonous and phosphinous acids are prepared by the eame methods as given above for other anhydrides. Only one such compound is k n o h , obtained in 63 per cent yield, b.p. 91-93'C./1.5 mm., by the following reaction (27) : CtHS(O)(OC*HdNa
+ (G&hPCl
+ NaCl
-+
GHQ(OGHdOP(G&h
The product ignites in air. B . REACI'IONS OF PHOSPHONOUS ANHYDRIDES
A. SYNTHESIS OF PHOSPHONOUS ANHYDRIDES
1. From phosphonous dichlorides with dialk yl phosphites Mixed anhydrides of phosphonous and phosphorous acids are obtained when ethylphosphonous dichloride is treated with a dialkyl phosphite under conditions normally used for esterification, i.e., employing the sodium derivative of the phosphite or a tertiary amine as an acid acceptor (2lj) :
The phosphonous anhydrides are sensitive to moisture and oxygen, and must be handled in B dry, inert atmosphere, They react vigorously with alkyl halides, giving quaternary phosphonium halides (26, 27) :
+
CtH6P[OP(OGH6)~1r CeHsBr
+
(C&W"r
The reaction is not a simple Arbuzov rearrangement, since the product is not one which would be expected of such a rearrangement. The following mechanism for the
Preparation from Product
CrHrP(OP(OGHr)r]r.................... G H I P ( O P ( O C I H ~ .) .~.).~. . . . . . . . . . . . . . . . GH1P[OP(0CiHriso)r]r . . . . . . . . . . . . . . . . .
Phospbonous dichloride
CrHsPClr CaHrPClr CrHrPCl:
1
Boiling Point
Dialkyl phosphite
Reference
or aodium phosphite
(GHfi0)aPONa (CrHiOhPONa (ho-C8HiO)rPONa
48
128-128/0.5 mm. 145-147/1 mm. 130-132/1 mm.
(26)
419
THE PHOSPHONOUS ACIlDB ALNDT H E I R DERIVATIVES
progressive displacement of phosphite groups has been suggested (26) :
+ (CzHs)rPOP(OGHs)s + CIHSI (CzHs)rP + CzHsI
CSHIP[OP(OCZH~)~]~ CiHsI 4 (CzHs)nPOP(OCzHs), -+
-+
+ (CtHbO)zP(O)I
(CiHs)sP f (CzHsO)rP(O)I (CiHdJ‘I
It will be noted that the first phosphorus atom, being the more easily quaternized, is the one that appears in the tetraethylphosphonium iodide. In mixed phosphinous-phosphonous anhydrides the phosphorus atom in the phosphinous portion is the more easily quaternized. The product of the reaction of CaHdP(OC2Hs)OP(CaH& with butyl bromide, then, is (CzHa)@4H&PBr and not CJ&”H&PBr (27). XI. REFERENCES (1) ABRAMOV, V. S.: Doklady Akad. Nauk S.S.S.R. 117, 811 (1957); Chem. Abstracts 52, 8038 (1958). V. S., AND KASHIRSKY, M. I.: J. Gen. Chem. (2) ABRAMOV, U.S.S.R. (Eng. Transl.) 28,3090 (1958). (3) ALLEN,J. F.: J. Am. Chem. Soc. 79,3071 (1957). 0. H.: J. Am. Chem. Soc. 77, (4) ALLEN,J. F., AND JOHNSON, 2871 (1955); British patents 783,697 and 784,985 (1957); Chem. Abstracts 52, 8194 and 8195 (1958). (6) ANAND, N., A N D TODD, A. R.: J. Chem. Soc. 1951,1807. H. H.: J. Am. Chem. SOC.75, 1576 (1953). (6) ANDERSON, (7) ANON.:Chem. Eng. News 30,4515 (1952). (8) ARBUZOV,A. E.: J. Russ. PhysXhem. Soc. 42,395 (1910); Chem. Abstracts 5,1397 (1911). A. E.: Zhur. ObshcheI Khim. 4, 898 (1934); (9) ARBUZOV, Chem. Abstracts 29, 2146 (1935). (10) ARBUZOV, A. E., AND ARBUZOV, B. A.: J. Rum. Phys.Chem. SOC.61, 1599 (1929); Chem. Abstracts 24, 5289 (1930). (11) ARBUZOV, A. E., AND ARBUZOVA, I.: J. Russ. Phys.-Chem. SOC.61, 1905 (1929); Chem. Abstracts 24,5289 (1930). (12) ARBUZOV,A. E., AND KAMAI,G.: J. R u m Phys.-Chem. SOC.61, 2037 (1929); Chem. Abstracts 24, 5736 (1930). A. E., AND KAMAI,G.: Zhur. ObshcheI Khim. (13) ARBUZOV, 17, 2149 (1957); Chem. Abstracts 42,4523 (1948). (14) ARBUZOV,A. E., KAMAI,G., AND BELOROSSOVA, 0. N.: Zhur. ObshcheI Khim. 15, 766 (1945); Chem. Abstracts 41,105 (1947). (15) ARBUZOV,A. E., KAMAI,G., A N D NESTEROV, L. V.: Trudy Kazan. Khim.-Tekhnol. Inst. im. S. M. Kirova 1951, No. 16, 17; Chem. Abstracts 51,5720 (1957). (16) ARBUZOV, A. E., AND RAZUMOV, A. I.: Izvest. Akad. Nauk S.S.S.R., Otdel. Khim. Nauk 1945, 167; Chem. Abstracts 40, 3411 (1946). (17) ARBUZOV,B. A,, A N D GRECHKIN, N. P.: J. Gen. Chem. U.S.S.R. (Eng. Transl.) 20, 113 (1950). B. A,, A N D GRECHKIN, N. P.: Bull. Acad. Sci. (18) ARBUZOV, U.S.S.R., Div. Chem. Sci. (Eng. Transl.) 1956, 429. (19) ARBUZOV, B. A., AND RIZPOLOZHENSKY, N. I.: Bull. Acad. Sci. U.S.S.R., Div. Chem. Sci. (Eng. Transl.) 1952, 765. B. A., AND RIZPOLOZHENSKY, N. I.: Bull. Acad. (20) ARBUZOV, Sci. U.S.S.R., Div. Chem. Sci. (Eng. Transl.) 1952, 843. B. A., AND RIZPOLOZHENSKY, N. I.: Doklady (21) ARBUZOV, Akad. Nauk S.S.S.R. 83, 581 (1952); Chem. Abstracts 47, 3226 (1953). (22) ARBUZOV,B. A., AND RIZPOLOZHENSKY, N. I.: Doklady Akad. Nauk S.S.S.R. 89, 291 (1953); Chem. Abstracts 48,7540 (1954).
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T H E PHOSPHONOUS ACIDS
421
AND T H E I R DEHIVATIVES
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